Freezing (other)
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Freezing is a
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 of ...
in which a
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, a ...
turns into a
solid Solid is one of the State of matter#Four fundamental states, four fundamental states of matter (the others being liquid, gas, and Plasma (physics), plasma). The molecules in a solid are closely packed together and contain the least amount o ...
when its
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied o ...
is lowered below its freezing point. In accordance with the internationally established definition, ''freezing'' means the solidification phase change of a liquid or the liquid content of a substance, usually due to cooling. For most substances, the melting and freezing points are the same temperature; however, certain substances possess differing solid-liquid transition temperatures. For example,
agar Agar ( or ), or agar-agar, is a jelly-like substance consisting of polysaccharides obtained from the cell walls of some species of red algae, primarily from ogonori (''Gracilaria'') and "tengusa" (''Gelidiaceae''). As found in nature, agar is ...
displays a
hysteresis Hysteresis is the dependence of the state of a system on its history. For example, a magnet may have more than one possible magnetic moment in a given magnetic field, depending on how the field changed in the past. Plots of a single component of ...
in its
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
and freezing point. It melts at and solidifies from .


Crystallization

Most liquids freeze by crystallization, formation of
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, macrosc ...
from the uniform liquid. This is a first-order thermodynamic
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 of ...
, which means that as long as solid and liquid coexist, the temperature of the whole system remains very nearly equal to the
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
due to the slow removal of heat when in contact with air, which is a poor heat conductor. Because of the
latent heat of fusion In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a s ...
, the freezing is greatly slowed and the temperature will not drop anymore once the freezing starts but will continue dropping once it finishes. Crystallization consists of two major events,
nucleation In thermodynamics, nucleation is the first step in the formation of either a new thermodynamic phase or structure via self-assembly or self-organization within a substance or mixture. Nucleation is typically defined to be the process that deter ...
and crystal growth. "Nucleation" is the step wherein the molecules start to gather into clusters, on the
nanometer 330px, Different lengths as in respect to the molecular scale. The nanometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: nm) or nanometer (American and British English spelling differences#-re ...
scale, arranging in a defined and periodic manner that defines the
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystal, crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pat ...
. "Crystal growth" is the subsequent growth of the nuclei that succeed in achieving the critical cluster size.


Supercooling

In spite of the
second law of thermodynamics The second law of thermodynamics is a physical law based on universal experience concerning heat and Energy transformation, energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects ( ...
, crystallization of pure liquids usually begins at a lower temperature than the
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
, due to high
activation energy In chemistry and physics, activation energy is the minimum amount of energy that must be provided for compounds to result in a chemical reaction. The activation energy (''E''a) of a reaction is measured in joules per mole (J/mol), kilojoules pe ...
of homogeneous nucleation. The creation of a nucleus implies the formation of an interface at the boundaries of the new phase. Some energy is expended to form this interface, based on the
surface energy In surface science, surface free energy (also interfacial free energy or surface energy) quantifies the disruption of intermolecular bonds that occurs when a surface is created. In solid-state physics, surfaces must be intrinsically less energe ...
of each phase. If a hypothetical nucleus is too small, the energy that would be released by forming its volume is not enough to create its surface, and nucleation does not proceed. Freezing does not start until the temperature is low enough to provide enough energy to form stable nuclei. In presence of irregularities on the surface of the containing vessel, solid or gaseous impurities, pre-formed solid crystals, or other nucleators,
heterogeneous nucleation Homogeneity and heterogeneity are concepts often used in the sciences and statistics relating to the uniformity of a substance or organism. A material or image that is homogeneous is uniform in composition or character (i.e. color, shape, size, ...
may occur, where some energy is released by the partial destruction of the previous interface, raising the supercooling point to be near or equal to the melting point. The melting point of
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
at 1 atmosphere of pressure is very close to , and in the presence of nucleating substances the freezing point of water is close to the melting point, but in the absence of nucleators water can
supercool 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 ...
to before freezing. Under high pressure (2,000
atmosphere An atmosphere () is a layer of gas or layers of gases that envelop a planet, and is held in place by the gravity of the planetary body. A planet retains an atmosphere when the gravity is great and the temperature of the atmosphere is low. A s ...
s) water will supercool to as low as before freezing.


Exothermicity

Freezing is almost always an
exothermic In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
process, meaning that as liquid changes into solid, heat and pressure are released. This is often seen as counter-intuitive, since the temperature of the material does not rise during freezing, except if the liquid were
supercooled 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 ...
. But this can be understood since heat must be continually removed from the freezing liquid or the freezing process will stop. The energy released upon freezing is a latent heat, and is known as the enthalpy of fusion and is exactly the same as the energy required to
melt Melt may refer to: Science and technology * Melting, in physics, the process of heating a solid substance to a liquid * Melt (manufacturing), the semi-liquid material used in steelmaking and glassblowing * Melt (geology), magma ** Melt inclusions, ...
the same amount of the solid. Low-temperature
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 the only known exception to the general rule.
Helium-3 Helium-3 (3He see also helion) is a light, stable isotope of helium with two protons and one neutron (the most common isotope, helium-4, having two protons and two neutrons in contrast). Other than protium (ordinary hydrogen), helium-3 is the ...
has a negative enthalpy of fusion at temperatures below 0.3 K.
Helium-4 Helium-4 () is a stable isotope of the element helium. It is by far the more abundant of the two naturally occurring isotopes of helium, making up about 99.99986% of the helium on Earth. Its nucleus is identical to an alpha particle, and consis ...
also has a very slightly negative enthalpy of fusion below 0.8 K. This means that, at appropriate constant pressures, heat must be ''added'' to these substances in order to freeze them.


Vitrification

Certain materials, such as
glass Glass is a non-crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling (quenching) of ...
and
glycerol Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...
, may harden without crystallizing; these are called
amorphous solid In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wit ...
s. Amorphous materials, as well as some polymers, do not have a freezing point, as there is no abrupt phase change at any specific temperature. Instead, there is a gradual change in their viscoelastic properties over a range of temperatures. Such materials are characterized by a glass transition that occurs at a
glass transition temperature The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle "glassy" state into a viscous or rubb ...
, which may be roughly defined as the "knee" point of the material's density vs. temperature graph. Because vitrification is a non-equilibrium process, it does not qualify as freezing, which requires an equilibrium between the crystalline and liquid state.


Expansion

The size of substances increases or expands on being heated. This increase in the size of a body due to heating is called thermal expansion .. Thermal expansion takes place in all objects and in all states of matter. However, different substances have different rates of expansion for the same rise in temperature.''


Freezing of living organisms

Many living organisms are able to tolerate prolonged periods of time at temperatures below the freezing point of water. Most living organisms accumulate
cryoprotectant A cryoprotectant is a substance used to protect biological tissue from freezing damage (i.e. that due to ice formation). Arctic and Antarctic insects, fish and amphibians create cryoprotectants (antifreeze, antifreeze compounds and antifreeze prot ...
s such as anti-nucleating proteins, polyols, and glucose to protect themselves against frost damage by sharp ice crystals. Most plants, in particular, can safely reach temperatures of −4 °C to −12 °C. Certain
bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...
, notably ''
Pseudomonas syringae ''Pseudomonas syringae'' is a rod-shaped, Gram-negative bacterium with polar flagella. As a plant pathogen, it can infect a wide range of species, and exists as over 50 different pathovars, all of which are available to researchers from internat ...
'', produce specialized proteins that serve as potent ice nucleators, which they use to force ice formation on the surface of various fruits and plants at about −2 °C. The freezing causes injuries in the epithelia and makes the nutrients in the underlying plant tissues available to the bacteria.


Bacteria

Three species of bacteria, ''
Carnobacterium pleistocenium ''Carnobacterium pleistocenium'' is a recently discovered bacterium from the arctic part of Alaska. It was found in permafrost, seemingly frozen there for 32,000 years. Melting the ice, however, brought these extremophiles back to life. This i ...
'', as well as ''
Chryseobacterium greenlandensis ''Chryseobacterium aquaticum'' is a Gram-negative, non- spore-forming and non-motile bacteria Non-motile bacteria are bacteria species that lack the ability and structures that would allow them to propel themselves, under their own power, thr ...
'' and ''
Herminiimonas glaciei ''Herminiimonas glaciei'' is a species of ultramicrobacterium in the family Oxalobacteraceae. These small gram-negative cells have a variable number of long flagella at the ends and sides of their rod-shaped bodies. With dimensions of 0.5–0. ...
'', have reportedly been revived after surviving for thousands of years frozen in ice.


Plants

Many plants undergo a process called hardening, which allows them to survive temperatures below 0 °C for weeks to months.


Animals

The nematode '' Haemonchus contortus'' can survive 44 weeks frozen at
liquid nitrogen Liquid nitrogen—LN2—is nitrogen in a liquid state at low temperature. Liquid nitrogen has a boiling point of about . It is produced industrially by fractional distillation of liquid air. It is a colorless, low viscosity liquid that is wide ...
temperatures. Other nematodes that survive at temperatures below 0 °C include '' Trichostrongylus colubriformis'' and '' Panagrolaimus davidi''. Many species of reptiles and amphibians survive freezing. Human gametes and 2-, 4- and 8-cell
embryos An embryo is an initial stage of development of a multicellular organism. In organisms that reproduce sexually, embryonic development is the part of the life cycle that begins just after fertilization of the female egg cell by the male sper ...
can survive freezing and are viable for up to 10 years, a process known as cryopreservation. Experimental attempts to freeze human beings for later revival are known as
cryonics Cryonics (from el, κρύος ''kryos'' meaning 'cold') is the low-temperature freezing (usually at ) and storage of human remains, with the speculative hope that resurrection may be possible in the future. Cryonics is regarded with skepticis ...
.


Food preservation

Freezing is a common method of
food preservation Food preservation includes processes that make food more resistant to microorganism growth and slow the oxidation of fats. This slows down the decomposition and rancidification process. Food preservation may also include processes that inhibit ...
that slows both food decay and the growth of micro-organisms. Besides the effect of lower temperatures on
reaction rate The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit ...
s, freezing makes water less available for
bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria were among ...
growth. Freezing is one of the oldest and most widely used methods of food preservation; since as long ago as 1842, freezing has been used in an ice and salt brine. In freezing, flavours, smell and nutritional content generally remain unchanged. Freezing became commercially applicable after the advent (introduction) of mechanical refrigeration. Freezing has been successfully employed for long term preservation of many foods providing a significantly extended shelf-life. Freezing preservation is generally regarded as superior to canning and dehydration with respect to retention in sensory attributes and nutritive attributes.


See also

* Degree of frost *
Directional freezing Directional freezing freezes from only one direction. Directional freezing can freeze water, from only one direction or side of a container, into clear ice. Directional freezing in a domestic freezer can be done by putting water in a insulated ...
* Flash freezing * Fractional freezing * Freezer * Freezing air temperature *
Frost Frost is a thin layer of ice on a solid surface, which forms from water vapor in an above-freezing atmosphere coming in contact with a solid surface whose temperature is below freezing, and resulting in a phase change from water vapor (a gas) ...
* Micro-pulling-down * Mpemba effect *
Phase diagram A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions (pressure, temperature, volume, etc.) at which thermodynamically distinct phases (such as solid, liquid or gaseous ...


Table


References


External links

* *
Video of an intermetallic compound solidifying/freezing
{{Authority control Phase transitions Atmospheric thermodynamics Heating, ventilation, and air conditioning Cryobiology Articles containing video clips