Allotropes of oxygen
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There are several known
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 ...
of oxygen. The most familiar is molecular oxygen (O2), present at significant levels in
Earth's atmosphere The atmosphere of Earth is the layer of gases, known collectively as air, retained by Earth's gravity that surrounds the planet and forms its planetary atmosphere. The atmosphere of Earth protects life on Earth by creating pressure allowing fo ...
and also known as dioxygen or
triplet oxygen Triplet oxygen, 3O2, refers to the ''S'' = 1 electronic ground state of molecular oxygen (dioxygen). It is the most stable and common allotrope of oxygen. Molecules of triplet oxygen contain two unpaired electrons, making triplet oxygen an unus ...
. Another is the highly reactive
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the lo ...
(O3). Others are: *Atomic oxygen (O1), a
free radical A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Ailments of unknown cause Biogerontology Biological processes Causes of death Cellular processes Gerontology Life extension Metabo ...
. * Singlet oxygen (O2*), one of two metastable states of molecular oxygen. * Tetraoxygen (O4), another metastable form. *
Solid oxygen Solid oxygen forms at normal atmospheric pressure at a temperature below 54.36 K (−218.79 °C, −361.82 °F). Solid oxygen O2, like liquid oxygen, is a clear substance with a light sky-blue color caused by absorption in the red part ...
, existing in six variously colored phases, of which one is and another one metallic.


Atomic oxygen

Atomic oxygen, denoted O(3P) or O(3P), is very reactive, as the single atoms of oxygen tend to quickly bond with nearby molecules. On Earth's surface, it exists naturally for a very short time. In
outer space Outer space, commonly shortened to space, is the expanse that exists beyond Earth and its atmosphere and between celestial bodies. Outer space is not completely empty—it is a near-perfect vacuum containing a low density of particles, pred ...
, the presence of ample
ultraviolet radiation Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation i ...
results in a
low Earth orbit A low Earth orbit (LEO) is an orbit around Earth with a period of 128 minutes or less (making at least 11.25 orbits per day) and an eccentricity less than 0.25. Most of the artificial objects in outer space are in LEO, with an altitude never mor ...
atmosphere in which 96% of the oxygen occurs in atomic form. Ryan D. McCulla, Saint Louis University (2010). /acswebcontent.acs.org/prfar/2010/reports/P11141.html "Atomic Oxygen O(3P): Photogeneration and Reactions with Biomolecules" "Out of Thin Air"
. NASA.gov. February 17, 2011.
Atomic oxygen has been detected on
Mars Mars is the fourth planet from the Sun and the second-smallest planet in the Solar System, only being larger than Mercury. In the English language, Mars is named for the Roman god of war. Mars is a terrestrial planet with a thin at ...
by
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,
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, and the
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observatory.


Dioxygen

The common allotrope of elemental oxygen on Earth, , is generally known as oxygen, but may be called ''dioxygen'', ''diatomic oxygen'', ''molecular oxygen'', or ''oxygen gas'' to distinguish it from the element itself and from the triatomic allotrope ''
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the lo ...
,'' . As a major component (about 21% by volume) of Earth's atmosphere, elemental oxygen is most commonly encountered in the diatomic form.
Aerobic organisms Aerobic means "requiring air," in which "air" usually means oxygen. Aerobic may also refer to * Aerobic exercise, prolonged exercise of moderate intensity * Aerobics, a form of aerobic exercise * Aerobic respiration, the aerobic process of cell ...
use atmospheric dioxygen as the terminal oxidant in
cellular respiration Cellular respiration is the process by which biological fuels are oxidised in the presence of an inorganic electron acceptor such as oxygen to produce large amounts of energy, to drive the bulk production of ATP. Cellular respiration may be des ...
in order to obtain chemical energy. The ground state of dioxygen is known as
triplet oxygen Triplet oxygen, 3O2, refers to the ''S'' = 1 electronic ground state of molecular oxygen (dioxygen). It is the most stable and common allotrope of oxygen. Molecules of triplet oxygen contain two unpaired electrons, making triplet oxygen an unus ...
, ''3''O2, because it has two unpaired electrons. The first excited state, singlet oxygen, ''1''O2, has no unpaired electrons and 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 ...
. The doublet state requires an odd number of electrons, and so cannot occur in dioxygen without gaining or losing electrons, such as in the
superoxide In chemistry, a superoxide is a compound that contains the superoxide ion, which has the chemical formula . The systematic name of the anion is dioxide(1−). The reactive oxygen ion superoxide is particularly important as the product of t ...
ion () or the dioxygenyl ion (). The ground state of has a bond length of 121  pm and a bond energy of 498 kJ/mol. It is a colourless gas with a boiling point of . It can be condensed from air by cooling with liquid nitrogen, which has a boiling point of . Liquid oxygen is pale blue in colour, and is quite markedly
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, ...
due to the unpaired electrons; liquid oxygen contained in a flask suspended by a string is attracted to a magnet.


Singlet oxygen

Singlet oxygen is the common name used for the two metastable states of molecular
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...
(O2) with higher energy than the ground state
triplet oxygen Triplet oxygen, 3O2, refers to the ''S'' = 1 electronic ground state of molecular oxygen (dioxygen). It is the most stable and common allotrope of oxygen. Molecules of triplet oxygen contain two unpaired electrons, making triplet oxygen an unus ...
. Because of the differences in their electron shells, singlet oxygen has different chemical and physical properties than triplet oxygen, including absorbing and emitting light at different wavelengths. It can be generated in a photosensitized process by energy transfer from dye molecules such as rose bengal, methylene blue or
porphyrins Porphyrins ( ) are a group of heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges (=CH−). The parent of porphyrin is porphine, a rare chemical compo ...
, or by chemical processes such as spontaneous decomposition of hydrogen trioxide in water or the reaction of
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3% ...
with hypochlorite.


Ozone

Triatomic oxygen (ozone, O3) is a very reactive allotrope of oxygen that is a pale blue gas at standard temperature and pressure. Liquid and solid O3 have a deeper blue color than ordinary O2, and they are unstable and explosive. Mellor 1939Cotton, F. Albert and Wilkinson, Geoffrey (1972). ''Advanced Inorganic Chemistry: A comprehensive Text''. (3rd Edition). New York, London, Sydney, Toronto: Interscience Publications. . In its gas phase, ozone is destructive to materials like
rubber Rubber, also called India rubber, latex, Amazonian rubber, ''caucho'', or ''caoutchouc'', as initially produced, consists of polymers of the organic compound isoprene, with minor impurities of other organic compounds. Thailand, Malaysia, an ...
and
fabric Textile is an umbrella term that includes various fiber-based materials, including fibers, yarns, filaments, threads, different fabric types, etc. At first, the word "textiles" only referred to woven fabrics. However, weaving is not th ...
and is damaging to lung tissue. Stwertka 1998, p.48 Traces of it can be detected as a pungent, chlorine-like smell,Chemistry Tutorial : Allotropes
from AUS-e-TUTE.com.au
coming from
electric motors An electric motor is an electrical machine that converts electrical energy into mechanical energy. Most electric motors operate through the interaction between the motor's magnetic field and electric current in a wire winding to generate forc ...
,
laser printer Laser printing is an electrostatic digital printing process. It produces high-quality text and graphics (and moderate-quality photographs) by repeatedly passing a laser beam back and forth over a negatively-charged cylinder called a "drum" to ...
s, and
photocopier A photocopier (also called copier or copy machine, and formerly Xerox machine, the generic trademark) is a machine that makes copies of documents and other visual images onto paper or plastic film quickly and cheaply. Most modern photocopiers ...
s, as it is formed whenever air is subjected to an electrical discharge. It was named "ozon" in 1840 by Christian Friedrich Schönbein, from ancient Greek ὄζειν (ozein: "to smell") plus the suffix ''-on'', commonly used at the time to designate a derived compound and anglicized as ''-one''. Ozone is thermodynamically unstable and tends to react toward the more common dioxygen form. It is formed by reaction of intact O2 with atomic oxygen produced when
UV radiation Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation i ...
in the
upper atmosphere Upper atmosphere is a collective term that refers to various layers of the atmosphere of the Earth above the troposphere and corresponding regions of the atmospheres of other planets, and includes: * The mesosphere, which on Earth lies between th ...
splits O2. Ozone absorbs strongly in the ultraviolet and in the stratosphere functions as a shield for the
biosphere The biosphere (from Greek βίος ''bíos'' "life" and σφαῖρα ''sphaira'' "sphere"), also known as the ecosphere (from Greek οἶκος ''oîkos'' "environment" and σφαῖρα), is the worldwide sum of all ecosystems. It can also ...
against mutagenic and other damaging effects of solar
UV radiation Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30  PHz) to 400 nm (750  THz), shorter than that of visible light, but longer than X-rays. UV radiation i ...
(see ozone layer). Tropospheric ozone is formed near the Earth's surface by the photochemical disintegration of
nitrogen dioxide Nitrogen dioxide is a chemical compound with the formula . It is one of several nitrogen oxides. is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year for use primarily in the productio ...
in the exhaust of
automobile A car or automobile is a motor vehicle with wheels. Most definitions of ''cars'' say that they run primarily on roads, seat one to eight people, have four wheels, and mainly transport people instead of goods. The year 1886 is regarde ...
s. Stwertka 1998, p.49
Ground-level ozone Ground-level ozone (O3), also known as surface-level ozone and tropospheric ozone, is a trace gas in the troposphere (the lowest level of the atmosphere of Earth, Earth's atmosphere), with an average concentration of 20–30 parts per billion by v ...
is an
air pollutant Air pollution is the contamination of air due to the presence of substances in the atmosphere that are harmful to the health of humans and other living beings, or cause damage to the climate or to materials. There are many different type ...
that is especially harmful for senior citizens, children, and people with heart and lung conditions such as emphysema,
bronchitis Bronchitis is inflammation of the bronchi (large and medium-sized airways) in the lungs that causes coughing. Bronchitis usually begins as an infection in the nose, ears, throat, or sinuses. The infection then makes its way down to the bronchi. ...
, and
asthma Asthma is a long-term inflammatory disease of the airways of the lungs. It is characterized by variable and recurring symptoms, reversible airflow obstruction, and easily triggered bronchospasms. Symptoms include episodes of wheezing, co ...
. The
immune system The immune system is a network of biological processes that protects an organism from diseases. It detects and responds to a wide variety of pathogens, from viruses to parasitic worms, as well as cancer cells and objects such as wood splint ...
produces ozone as an antimicrobial (see below).


Cyclic ozone

Cyclic ozone is a theoretically predicted O3 molecule in which its three atoms of oxygen bond in an equilateral triangle instead of an open angle.


Tetraoxygen

Tetraoxygen had been suspected to exist since the early 1900s, when it was known as oxozone. It was identified in 2001 by a team led by Fulvio Cacace at the University of Rome. The molecule was thought to be in one of the phases of
solid oxygen Solid oxygen forms at normal atmospheric pressure at a temperature below 54.36 K (−218.79 °C, −361.82 °F). Solid oxygen O2, like liquid oxygen, is a clear substance with a light sky-blue color caused by absorption in the red part ...
later identified as . Cacace's team suggested that probably consists of two dumbbell-like molecules loosely held together by induced dipole dispersion forces.


Phases of solid oxygen

There are six known distinct phases of solid oxygen. One of them is a dark-red cluster. When oxygen is subjected to a pressure of 96 GPa, it becomes
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
lic, in a similar manner to
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 ...
, and becomes more similar to the heavier chalcogens, such as
selenium Selenium is a chemical element with the symbol Se and atomic number 34. It is a nonmetal (more rarely considered a metalloid) with properties that are intermediate between the elements above and below in the periodic table, sulfur and tellurium, ...
(exhibiting a pink-red color in its elemental state),
tellurium Tellurium is a chemical element with the symbol Te and atomic number 52. It is a brittle, mildly toxic, rare, silver-white metalloid. Tellurium is chemically related to selenium and sulfur, all three of which are chalcogens. It is occasionall ...
and
polonium Polonium is a chemical element with the symbol Po and atomic number 84. Polonium is a chalcogen. A rare and highly radioactive metal with no stable isotopes, polonium is chemically similar to selenium and tellurium, though its metallic character ...
, both of which show significant metallic character. At very low temperatures, this phase also becomes
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 ...
.


References


Further reading

* * {{DEFAULTSORT:Allotropes of oxygen Oxygen