Freezing
Encyclopedia
Freezing or solidification is a phase change in which a liquid
turns into a solid
when its temperature
is lowered below its freezing point
. The reverse process is melting
.
All known liquids, except liquid helium
, freeze when the temperature is lowered enough. Liquid helium remains liquid at atmospheric pressure even at absolute zero
, and can be solidified only under pressure. For most substances, the melting and freezing points are the same temperature; however, certain substances possess differing solid–liquid transition temperatures. For example, agar
displays a hysteresis in its melting and freezing temperatures. It melts at 85 °C (185 °F) and solidifies from 31 °C to 40 °C (89.6 °F to 104 °F).
, formation of crystalline solid
from the uniform liquid. This is a first-order thermodynamic phase transition
, which means that, as long as solid and liquid coexist, the equilibrium temperature of the system remains constant and equal to the melting point
. Crystallization consists of two major events, nucleation
and crystal growth
. Nucleation is the step wherein the molecules start to gather into clusters, on the nanometer scale, arranging in a defined and periodic manner that defines the crystal structure
. The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size.
, crystallization of pure liquids usually begins at a lower temperature than the melting point
, due to high activation energy
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
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 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
at 1 atmosphere of pressure is very close to 0 °C (32 °F, 273.15 K), 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 super cool
to −40 °C (−40 °F, 233 K) before freezing. Under high pressure (2,000 atmosphere
s) water will super cool to as low as −70 °C (−94 °F, 203 K) before freezing.
process, meaning that as liquid changes into solid, heat and pressure is 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. 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
the same amount of the solid.
and glycerol
, may harden without crystallizing; these are called amorphous solid
s. Amorphous materials as well as some polymers do not have a true 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, which may be roughly defined as the "knee" point of the material's density vs. temperature graph.
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
, notably Pseudomonas syringae
, 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.
, as well as Chryseobacterium greenlandensis
and Herminiimonas glaciei
, have reportedly been revived after surviving for thousands of years frozen in ice.
, which allows them to survive temperatures below 0 °C for weeks to months.
can survive 44 weeks frozen at liquid nitrogen temperatures. Other nematodes that survive at temperatures below 0 °C include Trichostrongylus colubriformis and Panagrolaimus davidi. Many species of reptiles and amphibians survive freezing. See cryobiology
for a full discussion.
Human gametes and 2-, 4- and 8-cell embryos 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
.
that slows both food decay and the growth of micro-organisms. Besides the effect of lower temperatures on reaction rate
s, freezing makes water less available for bacteria
l growth.
Liquid
Liquid is one of the three classical states of matter . Like a gas, a liquid is able to flow and take the shape of a container. Some liquids resist compression, while others can be compressed. Unlike a gas, a liquid does not disperse to fill every space of a container, and maintains a fairly...
turns into a solid
Solid
Solid is one of the three classical states of matter . It is characterized by structural rigidity and resistance to changes of shape or volume. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire volume available to it like a...
when its temperature
Temperature
Temperature is a physical property of matter that quantitatively expresses the common notions of hot and cold. Objects of low temperature are cold, while various degrees of higher temperatures are referred to as warm or hot...
is lowered below its freezing point
Melting point
The melting point of a solid 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 on pressure and is usually specified at standard atmospheric pressure...
. The reverse process is melting
Melting
Melting, or fusion, is a physical process that results in the phase change of a substance from a solid to a liquid. The internal energy of a substance is increased, typically by the application of heat or pressure, resulting in a rise of its temperature to the melting point, at which the rigid...
.
All known liquids, except liquid helium
Liquid helium
Helium exists in liquid form only at extremely low temperatures. The boiling point and critical point depend on the isotope of the helium; see the table below for values. The density of liquid helium-4 at its boiling point and 1 atmosphere is approximately 0.125 g/mL Helium-4 was first liquefied...
, freeze when the temperature is lowered enough. Liquid helium remains liquid at atmospheric pressure even at absolute zero
Absolute zero
Absolute zero is the theoretical temperature at which entropy reaches its minimum value. The laws of thermodynamics state that absolute zero cannot be reached using only thermodynamic means....
, and can be solidified only under pressure. 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
Agar or agar-agar is a gelatinous substance derived from a polysaccharide that accumulates in the cell walls of agarophyte red algae. Throughout history into modern times, agar has been chiefly used as an ingredient in desserts throughout Asia and also as a solid substrate to contain culture medium...
displays a hysteresis in its melting and freezing temperatures. It melts at 85 °C (185 °F) and solidifies from 31 °C to 40 °C (89.6 °F to 104 °F).
Crystallization
Most liquids freeze by crystallizationCrystallization
Crystallization is the process of formation of solid crystals precipitating from a solution, melt or more rarely deposited directly from a gas. Crystallization is also a chemical solid–liquid separation technique, in which mass transfer of a solute from the liquid solution to a pure solid...
, formation of crystalline solid
Crystal
A crystal or crystalline solid is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. The scientific study of crystals and crystal formation is known as crystallography...
from the uniform liquid. This is a first-order thermodynamic phase transition
Phase transition
A phase transition is the transformation of a thermodynamic system from one phase or state of matter to another.A phase of a thermodynamic system and the states of matter have uniform physical properties....
, which means that, as long as solid and liquid coexist, the equilibrium temperature of the system remains constant and equal to the melting point
Melting point
The melting point of a solid 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 on pressure and is usually specified at standard atmospheric pressure...
. Crystallization consists of two major events, nucleation
Nucleation
Nucleation is the extremely localized budding of a distinct thermodynamic phase. Some examples of phases that may form by way of nucleation in liquids are gaseous bubbles, crystals or glassy regions. Creation of liquid droplets in saturated vapor is also characterized by nucleation...
and crystal growth
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 in the addition of new atoms, ions, or polymer strings into...
. Nucleation is the step wherein the molecules start to gather into clusters, on the nanometer scale, arranging in a defined and periodic manner that defines the crystal structure
Crystal structure
In mineralogy and crystallography, crystal structure is a unique arrangement of atoms or molecules in a crystalline liquid or solid. A crystal structure is composed of a pattern, a set of atoms arranged in a particular way, and a lattice exhibiting long-range order and symmetry...
. The 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 thermodynamicsSecond law of thermodynamics
The second law of thermodynamics is an expression of the tendency that over time, differences in temperature, pressure, and chemical potential equilibrate in an isolated physical system. From the state of thermodynamic equilibrium, the law deduced the principle of the increase of entropy and...
, crystallization of pure liquids usually begins at a lower temperature than the melting point
Melting point
The melting point of a solid 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 on pressure and is usually specified at standard atmospheric pressure...
, due to high activation energy
Activation energy
In chemistry, activation energy is a term introduced in 1889 by the Swedish scientist Svante Arrhenius that is defined as the energy that must be overcome in order for a chemical reaction to occur. Activation energy may also be defined as the minimum energy required to start a chemical reaction...
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
Surface energy
Surface energy quantifies the disruption of intermolecular bonds that occur when a surface is created. In the physics of solids, surfaces must be intrinsically less energetically favorable than the bulk of a material, otherwise there would be a driving force for surfaces to be created, removing...
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 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
Water is a chemical substance with the chemical formula H2O. A water molecule contains one oxygen and two hydrogen atoms connected by covalent bonds. Water is a liquid at ambient conditions, but it often co-exists on Earth with its solid state, ice, and gaseous state . Water also exists in a...
at 1 atmosphere of pressure is very close to 0 °C (32 °F, 273.15 K), and in the presence of nucleating substances
Nucleation
Nucleation is the extremely localized budding of a distinct thermodynamic phase. Some examples of phases that may form by way of nucleation in liquids are gaseous bubbles, crystals or glassy regions. Creation of liquid droplets in saturated vapor is also characterized by nucleation...
the freezing point of water is close to the melting point, but in the absence of nucleators water can super cool
Supercooling
Supercooling, also known as undercooling, is the process of lowering the temperature of a liquid or a gas below its freezing point without it becoming a solid....
to −40 °C (−40 °F, 233 K) before freezing. Under high pressure (2,000 atmosphere
Atmosphere (unit)
The standard atmosphere is an international reference pressure defined as 101325 Pa and formerly used as unit of pressure. For practical purposes it has been replaced by the bar which is 105 Pa...
s) water will super cool to as low as −70 °C (−94 °F, 203 K) before freezing.
Exothermicity
Freezing is an exothermicExothermic
In thermodynamics, the term exothermic describes a process or reaction that releases energy from the system, usually in the form of heat, but also in the form of light , electricity , or sound...
process, meaning that as liquid changes into solid, heat and pressure is 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. 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
Latent heat
Latent heat is the heat released or absorbed by a chemical substance or a thermodynamic system during a process that occurs without a change in temperature. A typical example is a change of state of matter, meaning a phase transition such as the melting of ice or the boiling of water. The term was...
, and is known as the enthalpy of fusion
Enthalpy of fusion
The enthalpy of fusion is the change in enthalpy resulting from heating one mole of a substance to change its state from a solid to a liquid. The temperature at which this occurs is the melting point....
and is exactly the same as the energy required to melt
Melting
Melting, or fusion, is a physical process that results in the phase change of a substance from a solid to a liquid. The internal energy of a substance is increased, typically by the application of heat or pressure, resulting in a rise of its temperature to the melting point, at which the rigid...
the same amount of the solid.
Vitrification
Certain materials, such as glassGlass
Glass is an amorphous solid material. Glasses are typically brittle and optically transparent.The most familiar type of glass, used for centuries in windows and drinking vessels, is soda-lime glass, composed of about 75% silica plus Na2O, CaO, and several minor additives...
and glycerol
Glycerol
Glycerol is a simple polyol compound. It is a colorless, odorless, viscous liquid that is widely used in pharmaceutical formulations. Glycerol has three hydroxyl groups that are responsible for its solubility in water and its hygroscopic nature. The glycerol backbone is central to all lipids...
, may harden without crystallizing; these are called amorphous solid
Amorphous solid
In condensed matter physics, an amorphous or non-crystalline solid is a solid that lacks the long-range order characteristic of a crystal....
s. Amorphous materials as well as some polymers do not have a true freezing point, as there is no abrupt phase change at any specific temperature. Instead, there is a gradual change in their viscoelastic
Viscoelasticity
Viscoelasticity is the property of materials that exhibit both viscous and elastic characteristics when undergoing deformation. Viscous materials, like honey, resist shear flow and strain linearly with time when a stress is applied. Elastic materials strain instantaneously when stretched and just...
properties over a range of temperatures. Such materials are characterized by a glass transition
Glass transition
The liquid-glass transition is the reversible transition in amorphous materials from a hard and relatively brittle state into a molten or rubber-like state. An amorphous solid that exhibits a glass transition is called a glass...
that occurs at a glass transition temperature, which may be roughly defined as the "knee" point of the material's density vs. temperature graph.
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 cryoprotectantCryoprotectant
A cryoprotectant is a substance that is used to protect biological tissue from freezing damage . Arctic and Antarctic insects, fish, amphibians and reptiles create cryoprotectants in their bodies to minimize freezing damage during cold winter periods. Insects most often use sugars or polyols as...
s such as anti-nucleating proteins
Antifreeze protein
Antifreeze proteins or ice structuring proteins refer to a class of polypeptides produced by certain vertebrates, plants, fungi and bacteria that permit their survival in subzero environments. AFPs bind to small ice crystals to inhibit growth and recrystallization of ice that would otherwise be...
, 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
Bacteria are a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria have a wide range of shapes, ranging from spheres to rods and spirals...
, notably Pseudomonas syringae
Pseudomonas syringae
Pseudomonas syringae is a rod shaped, Gram-negative bacterium with polar flagella. It is a plant pathogen which can infect a wide range of plant species, and exists as over 50 different pathovars, all of which are available to legitimate researches via international culture collections such as the...
, 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 pleistoceniumCarnobacterium pleistocenium
Carnobacterium pleistocenium is a type of 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 is the first case of an organism "coming back to...
, as well as Chryseobacterium greenlandensis
Chryseobacterium greenlandensis
Chryseobacterium greenlandensis is an Ultramicrobacteria species of bacteria that is able to live for long periods of time in habitats low-temperature, high-pressure, reduced-oxygen and nutrient-poor habitats. It is known to have survived for more than 120,000 years in an ice block in Greenland, at...
and Herminiimonas glaciei
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 0.5–0.9 by 0.3–0.4 µm, H. glaciei is roughly 10 to 50 times...
, have reportedly been revived after surviving for thousands of years frozen in ice.
Plants
Many plants undergo a process called hardeningHardening (botany)
Hardening in botany is the process by which an individual plant becomes tolerant to the effects of freezing during a period of weeks to months. It is a three stage process. During the first stage, carbohydrates are translocated to the roots of the plant and cell membrane permeability increases...
, which allows them to survive temperatures below 0 °C for weeks to months.
Animals
The nematode Haemonchus contortusHaemonchus contortus
Haemonchus contortus, also known as red stomach worm, wire worm or Barber's pole worm, is very common parasite and one the most pathogenic nematode of ruminants. Adult worms are attached to abomasal mucosa and feed on the blood...
can survive 44 weeks frozen at liquid nitrogen temperatures. Other nematodes that survive at temperatures below 0 °C include Trichostrongylus colubriformis and Panagrolaimus davidi. Many species of reptiles and amphibians survive freezing. See cryobiology
Cryobiology
Cryobiology is the branch of biology that studies the effects of low temperatures on living things. The word cryobiology is derived from the Greek words "cryo" = cold, "bios" = life, and "logos" = science. In practice, cryobiology is the study of biological material or systems at temperatures below...
for a full discussion.
Human gametes and 2-, 4- and 8-cell embryos can survive freezing and are viable for up to 10 years, a process known as cryopreservation
Cryopreservation
Cryopreservation is a process where cells or whole tissues are preserved by cooling to low sub-zero temperatures, such as 77 K or −196 °C . At these low temperatures, any biological activity, including the biochemical reactions that would lead to cell death, is effectively stopped...
.
Experimental attempts to freeze human beings for later revival are known as cryonics
Cryonics
Cryonics is the low-temperature preservation of humans and animals who can no longer be sustained by contemporary medicine, with the hope that healing and resuscitation may be possible in the future. Cryopreservation of people or large animals is not reversible with current technology...
.
Food preservation
Freezing is a common method of food preservationFood preservation
Food preservation is the process of treating and handling food to stop or slow down spoilage and thus allow for longer storage....
that slows both food decay and the growth of micro-organisms. Besides the effect of lower temperatures on reaction rate
Reaction rate
The reaction rate or speed of reaction for a reactant or product in a particular reaction is intuitively defined as how fast or slow a reaction takes place...
s, freezing makes water less available for bacteria
Bacteria
Bacteria are a large domain of prokaryotic microorganisms. Typically a few micrometres in length, bacteria have a wide range of shapes, ranging from spheres to rods and spirals...
l growth.
See also
- Degree of frostDegree of frostA degree of frost is a non-standard unit of measure for air temperature meaning degrees below melting point of water...
- Flash freezingFlash freezingFlash freezing refers to the process in various industries whereby objects are quickly frozen by subjecting them to cryogenic temperatures....
- FrostFrostFrost is the solid deposition of water vapor from saturated air. It is formed when solid surfaces are cooled to below the dew point of the adjacent air as well as below the freezing point of water. Frost crystals' size differ depending on time and water vapour available. Frost is also usually...
- Laser-heated pedestal growthLaser-heated pedestal growthLaser-heated pedestal growth is a crystal growth technique. The technique can be viewed as a miniature floating zone, where the heat source is replaced by a powerful CO2 or YAG laser...
- Micro-pulling-downMicro-pulling-down-Basics:The micro-pulling-down method is a crystal growth technique based on continuous transport of the melted substance through micro-channel made in a crucible bottom. Continuous solidification of the melt is progressed on a liquid/solid interface positioned under the crucible...
- Mpemba effectMpemba effectThe Mpemba effect is the observation that warmer water sometimes freezes faster than colder water. Although the observation has been verified, there is no single scientific explanation for the effect.-Historical observations:...
- Phase diagramPhase diagramA phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases can occur at equilibrium...