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Chalcogen

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The chalcogens (ore forming) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioactive elements polonium (Po) and livermorium (Lv). Often, oxygen is treated separately from the other chalcogens, sometimes even excluded from the scope of the term "chalcogen" altogether, due to its very different chemical behavior from sulfur, selenium, tellurium, and polonium. The word "chalcogen" is derived from a combination of the Greek word khalkόs (χαλκός) principally meaning copper (the term was also used for bronze, brass, any metal in the poetic sense, ore and coin), and the Latinized Greek word genēs, meaning born or produced.

Sulfur has been known since antiquity, and oxygen was recognized as an element in the 18th century. Selenium, tellurium and polonium were discovered in the 19th century, and livermorium in 2000. All of the chalcogens have six valence electrons, leaving them two electrons short of a full outer shell. Their most common oxidation states are −2, +2, +4, and +6. They have relatively low atomic radii, especially the lighter ones.

All of the naturally occurring chalcogens have some role in biological functions, either as a nutrient or a toxin. Selenium is an important nutrient (among others as a building block of selenocysteine) but is also commonly toxic. Tellurium often has unpleasant effects (although some organisms can use it), and polonium (especially the isotope polonium-210) is always harmful as a result of its radioactivity.

Sulfur has more than 20 allotropes, oxygen has nine, selenium has at least eight, polonium has two, and only one crystal structure of tellurium has so far been discovered. There are numerous organic chalcogen compounds. Not counting oxygen, organic sulfur compounds are generally the most common, followed by organic selenium compounds and organic tellurium compounds. This trend also occurs with chalcogen pnictides and compounds containing chalcogens and carbon group elements.

Oxygen is generally obtained by separation of air into nitrogen and oxygen. Sulfur is extracted from oil and natural gas. Selenium and tellurium are produced as byproducts of copper refining. Polonium is most available in naturally occurring actinide-containing materials. Livermorium has been synthesized in particle accelerators. The primary use of elemental oxygen is in steelmaking. Sulfur is mostly converted into sulfuric acid, which is heavily used in the chemical industry. Selenium's most common application is glassmaking. Tellurium compounds are mostly used in optical disks, electronic devices, and solar cells. Some of polonium's applications are due to its radioactivity.

Atomic and physical
Chalcogens show similar patterns in electron configuration, especially in the outermost shells, where they all have the same number of valence electrons, resulting in similar trends in chemical behavior:

All chalcogens have six valence electrons. All of the solid, stable chalcogens are soft and do not conduct heat well. Electronegativity decreases towards the chalcogens with higher atomic numbers. Density, melting and boiling points, and atomic and ionic radii tend to increase towards the chalcogens with higher atomic numbers.

Isotopes
Out of the six known chalcogens, one (oxygen) has an atomic number equal to a nuclear magic number, which means that their atomic nuclei tend to have increased stability towards radioactive decay. Oxygen has three stable isotopes, and 14 unstable ones. Sulfur has four stable isotopes, 20 radioactive ones, and one isomer. Selenium has six observationally stable or nearly stable isotopes, 26 radioactive isotopes, and 9 isomers. Tellurium has eight stable or nearly stable isotopes, 31 unstable ones, and 17 isomers. Polonium has 42 isotopes, none of which are stable. It has an additional 28 isomers. In addition to the stable isotopes, some radioactive chalcogen isotopes occur in nature, either because they are decay products, such as 210Po, because they are primordial, such as 82Se, because of cosmic ray spallation, or via nuclear fission of uranium. Livermorium isotopes 290Lv through 293Lv have been discovered; the most stable livermorium isotope is 293Lv, which has a half-life of 0.061 seconds.

With the exception of oxygen and livermorium, all chalcogens have at least one naturally occurring radioisotope, sulfur has trace 35S, selenium has 82Se, tellurium has 128Te and 130Te, and polonium has 210Po.

Among the lighter chalcogens (oxygen and sulfur), the most neutron-poor isotopes undergo proton emission, the moderately neutron-poor isotopes undergo electron capture or β+ decay, the moderately neutron-rich isotopes undergo β− decay, and the most neutron rich isotopes undergo neutron emission. The middle chalcogens (selenium and tellurium) have similar decay tendencies as the lighter chalcogens, but no proton-emitting isotopes have been observed, and some of the most neutron-deficient isotopes of tellurium undergo alpha decay. Polonium isotopes tend to decay via alpha or beta decay. Isotopes with nonzero nuclear spins are more abundant in nature among the chalcogens selenium and tellurium than they are with sulfur.

Allotropes

Oxygen's most common allotrope is diatomic oxygen, or O2, a reactive paramagnetic molecule that is ubiquitous to aerobic organisms and has a blue color in its liquid state. Another allotrope is O3, or ozone, which is three oxygen atoms bonded together in a bent formation. There is also an allotrope called tetraoxygen, or O4, and six allotropes of solid oxygen including "red oxygen", which has the formula O8.

Sulfur has over 20 known allotropes, which is more than any other element except carbon. The most common allotropes are in the form of eight-atom rings, but other molecular allotropes that contain as few as two atoms or as many as 20 are known. Other notable sulfur allotropes include rhombic sulfur and monoclinic sulfur. Rhombic sulfur is the more stable of the two allotropes. Monoclinic sulfur takes the form of long needles and is formed when liquid sulfur is cooled to slightly below its melting point. The atoms in liquid sulfur are generally in the form of long chains, but above 190 °C, the chains begin to break down. If liquid sulfur above 190 °C is frozen very rapidly, the resulting sulfur is amorphous or "plastic" sulfur. Gaseous sulfur is a mixture of diatomic sulfur (S2) and 8-atom rings.

Selenium has at least eight distinct allotropes. The gray allotrope, commonly referred to as the "metallic" allotrope, despite not being a metal, is stable and has a hexagonal crystal structure. The gray allotrope of selenium is soft, with a Mohs hardness of 2, and brittle. Four other allotropes of selenium are metastable. These include two monoclinic red allotropes and two amorphous allotropes, one of which is red and one of which is black. The red allotrope converts to the black allotrope in the presence of heat. The gray allotrope of selenium is made from spirals on selenium atoms, while one of the red allotropes is made of stacks of selenium rings (Se8).

Tellurium is not known to have any allotropes, although its typical form is hexagonal. Polonium has two allotropes, which are known as α-polonium and β-polonium. α-polonium has a cubic crystal structure and converts to the rhombohedral β-polonium at 36 °C.

The chalcogens have varying crystal structures. Oxygen's crystal structure is monoclinic, sulfur's is orthorhombic, selenium and tellurium have the hexagonal crystal structure, while polonium has a cubic crystal structure.

Chemical
Oxygen, sulfur, and selenium are nonmetals, and tellurium is a metalloid, meaning that its chemical properties are between those of a metal and those of a nonmetal. It is not certain whether polonium is a metal or a metalloid. Some sources refer to polonium as a metalloid, although it has some metallic properties. Also, some allotropes of selenium display characteristics of a metalloid, even though selenium is usually considered a nonmetal. Even though oxygen is a chalcogen, its chemical properties are different from those of other chalcogens. One reason for this is that the heavier chalcogens have vacant d-orbitals. Oxygen's electronegativity is also much higher than those of the other chalcogens. This makes oxygen's electric polarizability several times lower than those of the other chalcogens.

For covalent bonding a chalcogen may accept two electrons according to the octet rule, leaving two lone pairs. When an atom forms two single bonds, they form an angle between 90° and 120°. In 1+ cations, such as H3O+, a chalcogen forms three molecular orbitals arranged in a trigonal pyramidal fashion and one lone pair. Double bonds are also common in chalcogen compounds, for example in chalcogenates (see below).

The oxidation number of the most common chalcogen compounds with positive metals is −2. However the tendency for chalcogens to form compounds in the −2 state decreases towards the heavier chalcogens. Other oxidation numbers, such as −1 in pyrite and peroxide, do occur. The highest formal oxidation number is +6. This oxidation number is found in sulfates, selenates, tellurates, polonates, and their corresponding acids, such as sulfuric acid.

Oxygen is the most electronegative element except for fluorine, and forms compounds with almost all of the chemical elements, including some of the noble gases. It commonly bonds with many metals and metalloids to form oxides, including iron oxide, titanium oxide, and silicon oxide. Oxygen's most common oxidation state is −2, and the oxidation state −1 is also relatively common. With hydrogen it forms water and hydrogen peroxide. Organic oxygen compounds are ubiquitous in organic chemistry.

Sulfur's oxidation states are −2, +2, +4, and +6. Sulfur-containing analogs of oxygen compounds often have the prefix thio-. Sulfur's chemistry is similar to oxygen's, in many ways. One difference is that sulfur-sulfur double bonds are far weaker than oxygen-oxygen double bonds, but sulfur-sulfur single bonds are stronger than oxygen-oxygen single bonds. Organic sulfur compounds such as thiols have a strong specific smell, and a few are utilized by some organisms.

Selenium's oxidation states are −2, +4, and +6. Selenium, like most chalcogens, bonds with oxygen. There are some organic selenium compounds, such as selenoproteins. Tellurium's oxidation states are −2, +2, +4, and +6. Tellurium forms the oxides tellurium monoxide, tellurium dioxide, and tellurium trioxide. Polonium's oxidation states are +2 and +4.

There are many acids containing chalcogens, including sulfuric acid, sulfurous acid, selenic acid, and telluric acid. All hydrogen chalcogenides are toxic except for water. Oxygen ions often come in the forms of oxide ions (O(2-)), peroxide ions (O2(2-)), and hydroxide ions (OH-). Sulfur ions generally come in the form of sulfides (S(2-)), bisulfides (SH-), sulfites (SO3(2-)), sulfates (SO4(2-)), and thiosulfates (S2O3(2-)). Selenium ions usually come in the form of selenides (Se(2-)), selenites (SeO3(2-)) and selenates (SeO4(2-)). Tellurium ions often come in the form of tellurates (TeO4(2-)). Molecules containing metal bonded to chalcogens are common as minerals. For example, pyrite (FeS2) is an iron ore, and the rare mineral calaverite is the ditelluride (Au, Ag)Te2.

Although all group 16 elements of the periodic table, including oxygen, can be defined as chalcogens, oxygen and oxides are usually distinguished from chalcogens and chalcogenides. The term chalcogenide is more commonly reserved for sulfides, selenides, and tellurides, rather than for oxides.

Except for polonium, the chalcogens are all fairly similar to each other chemically. They all form X2− ions when reacting with electropositive metals.

Sulfide minerals and analogous compounds produce gases upon reaction with oxygen.

With halogens
Chalcogens also form compounds with halogens known as chalcohalides, or chalcogen halides. The majority of simple chalcogen halides are well-known and widely used as chemical reagents. However, more complicated chalcogen halides, such as sulfenyl, sulfonyl, and sulfuryl halides, are less well known to science. Out of the compounds consisting purely of chalcogens and halogens, there are a total of 13 chalcogen fluorides, nine chalcogen chlorides, eight chalcogen bromides, and six chalcogen iodides that are known. The heavier chalcogen halides often have significant molecular interactions. Sulfur fluorides with low valences are fairly unstable and little is known about their properties. However, sulfur fluorides with high valences, such as sulfur hexafluoride, are stable and well-known. Sulfur tetrafluoride is also a well-known sulfur fluoride. Certain selenium fluorides, such as selenium difluoride, have been produced in small amounts. The crystal structures of both selenium tetrafluoride and tellurium tetrafluoride are known. Chalcogen chlorides and bromides have also been explored. In particular, selenium dichloride and sulfur dichloride can react to form organic selenium compounds. Dichalcogen dihalides, such as Se2Cl2 also are known to exist. There are also mixed chalcogen-halogen compounds. These include SeSX, with X being chlorine or bromine. Such compounds can form in mixtures of sulfur dichloride and selenium halides. These compounds have been fairly recently structurally characterized, as of 2008. In general, diselenium and disulfur chlorides and bromides are useful chemical reagents. Chalcogen halides with attached metal atoms are soluble in organic solutions. One example of such a compound is MoS2Cl3. Unlike selenium chlorides and bromides, selenium iodides have not been isolated, as of 2008, although it is likely that they occur in solution. Diselenium diiodide, however, does occur in equilibrium with selenium atoms and iodine molecules. Some tellurium halides with low valences, such as Te2Cl2 and Te2Br2, form polymers when in the solid state. These tellurium halides can be synthesized by the reduction of pure tellurium with superhydride and reacting the resulting product with tellurium tetrahalides. Ditellurium dihalides tend to get less stable as the halides become lower in atomic number and atomic mass. Tellurium also forms iodides with even fewer iodine atoms than diiodides. These include TeI and Te2I. These compounds have extended structures in the solid state. Halogens and chalcogens can also form halochalcogenate anions.

Organic
Alcohols, phenols and other similar compounds contain oxygen. However, in thiols, selenols and tellurols; sulfur, selenium, and tellurium replace oxygen. Thiols are better known than selenols or tellurols. Aside from alcohols, thiols are the most stable chalcogenols and tellurols are the least stable, being unstable in heat or light. Other organic chalcogen compounds include thioethers, selenoethers and telluroethers. Some of these, such as dimethyl sulfide, diethyl sulfide, and dipropyl sulfide are commercially available. Selenoethers are in the form of R2Se or RSeR. Telluroethers such as dimethyl telluride are typically prepared in the same way as thioethers and selenoethers. Organic chalcogen compounds, especially organic sulfur compounds, have the tendency to smell unpleasant. Dimethyl telluride also smells unpleasant, and selenophenol is renowned for its "metaphysical stench". There are also thioketones, selenoketones, and telluroketones. Out of these, thioketones are the most well-studied with 80% of chalcogenoketones papers being about them. Selenoketones make up 16% of such papers and telluroketones make up 4% of them. Thioketones have well-studied non-linear electric and photophysical properties. Selenoketones are less stable than thioketones and telluroketones are less stable than selenoketones. Telluroketones have the highest level of polarity of chalcogenoketones.

With metals
There is a very large number of metal chalcogenides. There are also ternary compounds containing alkali metals and transition metals. Highly metal-rich metal chalcogenides, such as Lu7Te and Lu8Te have domains of the metal's crystal lattice containing chalcogen atoms. While these compounds do exist, analogous chemicals that contain lanthanum, praseodymium, gadolinium, holmium, terbium, or ytterbium have not been discovered, as of 2008. The boron group metals aluminum, gallium, and indium also form bonds to chalcogens. The Ti3+ ion forms chalcogenide dimers such as TiTl5Se8. Metal chalcogenide dimers also occur as lower tellurides, such as Zr5Te6.

Elemental chalcogens react with certain lanthanide compounds to form lanthanide clusters rich in chalcogens. Uranium(IV) chalcogenol compounds also exist. There are also transition metal chalcogenols which have potential to serve as catalysts and stabilize nanoparticles.

With pnictogens
Compounds with chalcogen-phosphorus bonds have been explored for more than 200 years. These compounds include unsophisticated phosphorus chalcogenides as well as large molecules with biological roles and phosphorus-chalcogen compounds with metal clusters. These compounds have numerous applications, including organo-phosphate insecticides, strike-anywhere matches and quantum dots. A total of 130,000 compounds with at least one phosphorus-sulfur bond, 6000 compounds with at least one phosphorus-selenium bond, and 350 compounds with at least one phosphorus-tellurium bond have been discovered. The decrease in the number of chalcogen-phosphorus compounds further down the periodic table is due to diminishing bond strength. Such compounds tend to have at least one phosphorus atom in the center, surrounded by four chalcogens and side chains. However, some phosphorus-chalcogen compounds also contain hydrogen (such as secondary phosphine chalcogenides) or nitrogen (such as dichalcogenoimidodiphosphates). Phosphorus selenides are typically harder to handle that phosphorus sulfides, and compounds in the form PxTey have not been discovered. Chalcogens also bond with other pnictogens, such as arsenic, antimony, and bismuth. Heavier chalcogen pnictides tend to form ribbon-like polymers instead of individual molecules. Chemical formulas of these compounds include Bi2S3 and Sb2Se3. Ternary chalcogen pnictides are also known. Examples of these include P4O6Se and P3SbS3. salts containing chalcogens and pnictogens also exist. Almost all chalcogen pnictide salts are typically in the form of [PnxE4x]3−, where Pn is a pnictogen and E is a chalcogen. Tertiary phosphines can react with chalcogens to form compounds in the form of R3PE, where E is a chalcogen. When E is sulfur, these compounds are relatively stable, but they are less so when E is selenium or tellurium. Similarly, secondary phosphines can react with chalcogens to form secondary phosphine chalcogenides. However, these compounds are in a state of equilibrium with chalcogenophosphinous acid. Secondary phosphine chalcogenides are weak acids. Binary compounds consisting of antimony or arsenic and a chalcogen. These compounds tend to be colorful and can be created by a reaction of the constituent elements at temperatures of 500 to 900 C.

Other
Chalcogens form single bonds and double bonds with other carbon group elements than carbon, such as silicon, germanium, and tin. Such compounds typically form from a reaction of carbon group halides and chalcogenol salts or chalcogenol bases. Cyclic compounds with chalcogens, carbon group elements, and boron atoms exist, and occur from the reaction of boron dichalcogenates and carbon group metal halides. Compounds in the form of M-E, where M is silicon, germanium, or tin, and E is sulfur, selenium or tellurium have been discovered. These form when carbon group hydrides react or when heavier versions of carbenes react. Sulfur and tellurium can bond with organic compounds containing both silicon and phosphorus.

All of the chalcogens form hydrides. In some cases this occurs with chalcogens bonding with two hydrogen atoms. However tellurium hydride and polonium hydride are both volatile and highly labile. Also, oxygen can bond to hydrogen in a 1:1 ratio as in hydrogen peroxide, but this compound is unstable.

Chalcogen compounds form a number of interchalcogens. For instance, sulfur forms the toxic sulfur dioxide and sulfur trioxide. Tellurium also forms oxides. There are some chalcogen sulfides as well. These include selenium sulfide, an ingredient in some shampoos.

Since 1990, a number of borides with chalcogens bonded to them have been detected. The chalcogens in these compounds are mostly sulfur, although some do contain selenium instead. One such chalcogen boride consists of two molecules of dimethyl sulfide attached to a boron-hydrogen molecule. Other important boron-chalcogen compounds include macropolyhedral systems. Such compounds tend to feature sulfur as the chalcogen. There are also chalcogen borides with two, three, or four chalcogens. Many of these contain sulfur but some, such as Na2B2Se7 contain selenium instead.

Early discoveries
Sulfur has been known since ancient times and is mentioned in the Bible fifteen times. It was known to the ancient Greeks and commonly mined by the ancient Romans. In the Middle Ages, it was a key part of alchemical experiments. In the 1700s and 1800s, scientists Joseph Louis Gay-Lussac and Louis-Jacques Thénard proved sulfur to be a chemical element.

Early attempts to separate oxygen from air were hampered by the fact that air was thought of as a single element up to the 17th and 18th centuries. Robert Hooke, Mikhail Lomonosov, Ole Borch, and Pierre Bayden all successfully created oxygen, but did not realize it at the time. Oxygen was discovered by Joseph Priestley in 1774 when he focused sunlight on a sample of mercuric oxide and collected the resulting gas. Carl Wilhelm Scheele had also created oxygen in 1771 by the same method, but Scheele did not publish his results until 1777.

Tellurium was first discovered in 1783 by Franz Joseph Müller von Reichenstein. He discovered tellurium in a sample of what is now known as calaverite. Müller assumed at first that the sample was pure antimony, but tests he ran on the sample did not agree with this. Muller then guessed that the sample was bismuth sulfide, but tests confirmed that the sample was not that. For some years, Muller pondered the problem. Eventually he realized that the sample was gold bonded with an unknown element. In 1796, Müller sent part of the sample to the German chemist Martin Klaproth, who purified the undiscovered element. Klaproth decided to call the element tellurium after the Latin word for earth.

Selenium was discovered in 1817 by Jöns Jacob Berzelius. Berzelius noticed a reddish-brown sediment at a sulfuric acid manufacturing plant. The sample was thought to contain arsenic. Berzelius initially thought that the sediment contained tellurium, but came to realize that it also contained a new element, which he named selenium after the Greek moon goddess Selene.

Periodic table placing

Three of the chalcogens (sulfur, selenium, and tellurium) were part of the discovery of periodicity, as they are among a series of triads of elements in the same group that were noted by Johann Wolfgang Döbereiner as having similar properties. Around 1865 John Newlands produced a series of papers where he listed the elements in order of increasing atomic weight and similar physical and chemical properties that recurred at intervals of eight; he likened such periodicity to the octaves of music. His version included a "group b" consisting of oxygen, sulfur, selenium, tellurium, and osmium.

After 1869, Dmitri Mendeleev proposed his periodic table placing oxygen at the top of "group VI" above sulfur, selenium, and tellurium. Chromium, molybdenum, tungsten, and uranium were sometimes included in this group, but they would be later rearranged as part of group VIB; uranium would later be moved to the actinide series. Oxygen, along with sulfur, selenium, tellurium, and later polonium would be grouped in group VIA, until the group's name was changed to group 16 in 1988.

Modern discoveries
In the late 19th century, Marie Curie and Pierre Curie discovered that a sample of pitchblende was emitting four times as much radioactivity as could be explained by the presence of uranium alone. The Curies gathered several tons of pitchblende and refined it for several months until they had a pure sample of polonium. The discovery officially took place in 1898. Prior to the invention of particle accelerators, the only way to produce polonium was to extract it over several months from uranium ore.

The first attempt at creating livermorium was from 1976 to 1977 at the LBNL, who bombarded curium-248 with calcium-48, but were not successful. After several failed attempts in 1977, 1998, and 1999 by research groups in Russia, Germany, and the US, livermorium was created successfully in 2000 at the Joint Institute for Nuclear Research by bombarding curium-248 atoms with calcium-48 atoms. The element was known as ununhexium until it was officially named livermorium in 2012.

Names and etymology
In the 19th century, Jons Jacob Berzelius suggested calling the elements in group 16 "amphigens", as the elements in the group formed amphid salts (salts of oxyacids. Formerly regarded as composed of two oxides, an acid and a basic oxide) The term received some use in the early 1800s but is now obsolete. The name chalcogen comes from the Greek words χαλκος (chalkos, literally "copper"), and γενές (genes, born, gender, kindle). It was first used in 1932 by Wilhelm Biltz's group at Leibniz University Hannover, where it was proposed by Werner Fischer. The word "chalcogen" gained popularity in Germany during the 1930s because the term was analogous to "halogen". Although the literal meanings of the modern Greek words imply that chalcogen means "copper-former", this is misleading because the chalcogens have nothing to do with copper in particular. "Ore-former" has been suggested as a better translation, as the vast majority of metal ores are chalcogenides and the word χαλκος in ancient Greek was associated with metals and metal-bearing rock in general; copper, and its alloy bronze, was one of the first metals to be used by humans.

Oxygen's name comes from the Greek words oxy genes, meaning "acid-forming". Sulfur's name comes from either the Latin word sulfurium or the Sanskrit word sulvere; both of those terms are ancient words for sulfur. Selenium is named after the Greek goddess of the moon, Selene, to match the previously discovered element tellurium, whose name comes from the Latin word telus, meaning earth. Polonium is named after Marie Curie's country of birth, Poland. Livermorium is named for the Lawrence Livermore National Laboratory.

Occurrence
The four lightest chalcogens (oxygen, sulfur, selenium, and tellurium) are all primordial elements on Earth. Sulfur and oxygen occur as constituent copper ores and selenium and tellurium occur in small traces in such ores. Polonium forms naturally from the decay of other elements, even though it is not primordial. Livermorium does not occur naturally at all.

Oxygen makes up 21% of the atmosphere by weight, 89% of water by weight, 46% of the Earth's crust by weight, and 65% of the human body. Oxygen also occurs in many minerals, being found in all oxide minerals and hydroxide minerals, and in numerous other mineral groups. Stars of at least eight times the mass of the Sun also produce oxygen in their cores via nuclear fusion. Oxygen is the third-most abundant element in the universe, making up 1% of the universe by weight.

Sulfur makes up 0.035% of the Earth's crust by weight, making it the 17th most abundant element there and makes up 0.25% of the human body. It is a major component of soil. Sulfur makes up 870 parts per million of seawater and about 1 part per billion of the atmosphere. Sulfur can be found in elemental form or in the form of sulfide minerals, sulfate minerals, or sulfosalt minerals. Stars of at least 12 times the mass of the Sun produce sulfur in their cores via nuclear fusion. Sulfur is the tenth most abundant element in the universe, making up 500 parts per million of the universe by weight.

Selenium makes up 0.05 parts per million of the Earth's crust by weight. This makes it the 67th most abundant element in the Earth's crust. Selenium makes up on average 5 parts per million of the soils. Seawater contains around 200 parts per trillion of selenium. The atmosphere contains 1 nanogram of selenium per cubic meter. There are mineral groups known as selenates and selenites, but there are not many minerals in these groups. Selenium is not produced directly by nuclear fusion. Selenium makes up 30 parts per billion of the universe by weight.

There are only 5 parts per billion of tellurium in the Earth's crust and 15 parts per billion of tellurium in seawater. Tellurium is one of the eight or nine least abundant elements in the Earth's crust. There are a few dozen tellurate minerals and telluride minerals, and tellurium occurs in some minerals with gold, such as sylvanite and calaverite. Tellurium makes up 9 parts per billion of the universe by weight.

Polonium only occurs in trace amounts on Earth, via radioactive decay of uranium and thorium. It is present in uranium ores in concentrations of 100 micrograms per metric ton. Very minute amounts of polonium exist in the soil and thus in most food, and thus in the human body. The Earth's crust contains less than 1 part per billion of polonium, making it one of the ten rarest metals on Earth.

Livermorium is always produced artificially in particle accelerators. Even when it is produced, only a small number of atoms are synthesized at a time.

Chalcophile elements
Chalcophile elements are those that remain on or close to the surface because they combine readily with chalcogens other than oxygen, forming compounds which do not sink into the core. Chalcophile ("chalcogen-loving") elements in this context are those metals and heavier nonmetals that have a low affinity for oxygen and prefer to bond with the heavier chalcogen sulfur as sulfides. Because sulfide minerals are much denser than the silicate minerals formed by lithophile elements, chalcophile elements separated below the lithophiles at the time of the first crystallisation of the Earth's crust. This has led to their depletion in the Earth's crust relative to their solar abundances, though this depletion has not reached the levels found with siderophile elements.

Production
Approximately 100 million metric tons of oxygen are produced yearly. Oxygen is most commonly produced by fractional distillation, in which air is cooled to a liquid, then warmed, allowing all the components of air except for oxygen to turn to gases and escape. Fractionally distilling air several times can produce 99.5% pure oxygen. Another method with which oxygen is produced is to send a stream of dry, clean air through a bed of molecular sieves made of zeolite, which absorbs the nitrogen in the air, leaving 90 to 93% pure oxygen.

Sulfur can be mined in its elemental form, although this method is no longer as popular as it used to be. In 1865 a large deposit of elemental sulfur was discovered in the U.S. states of Louisiana and Texas, but it was difficult to extract at the time. In the 1890s, Herman Frasch came up with the solution of liquefying the sulfur with superheated steam and pumping the sulfur up to the surface. These days sulfur is instead more often extracted from oil, natural gas, and tar.

The world production of selenium is around 1500 metric tons per year, out of which roughly 10% is recycled. Japan is the largest producer, producing 800 metric tons of selenium per year. Other large producers include Belgium (300 metric tons per year), the United States (over 200 metric tons per year), Sweden (130 metric tons per year), and Russia (100 metric tons per year). Selenium can be extracted from the waste from the process of electrolytically refining copper. Another method of producing selenium is to farm selenium-gathering plants such as milk vetch. This method could produce three kilograms of selenium per acre, but is not commonly practiced.

Tellurium is mostly produced as a by-product of the processing of copper. Tellurium can also be refined by electrolytic reduction of sodium telluride. The world production of tellurium is between 150 and 200 metric tons per year. The United States is one of the largest producers of tellurium, producing around 50 metric tons per year. Peru, Japan, and Canada are also large producers of tellurium.

Until the creation of nuclear reactors, all polonium had to be extracted from uranium ore. In modern times, most isotopes of polonium are produced by bombarding bismuth with neutrons. Polonium can also be produced by high neutron fluxes in nuclear reactors. Approximately 100 grams of polonium are produced yearly. All the polonium produced for commercial purposes is made in the Ozersk nuclear reactor in Russia. From there, it is taken to Samara, Russia for purification, and from there to St. Petersburg for distribution. The United States is the largest consumer of polonium.

All livermorium is produced artificially in particle accelerators. The first successful production of livermorium was achieved by bombarding curium-248 atoms with calcium-48 atoms. As of 2011, roughly 25 atoms of livermorium had been synthesized.

Applications
Metabolism is the most important source and use of oxygen. Minor industrial uses include Steelmaking (55% of all purified oxygen produced), the chemical industry (25% of all purified oxygen), medical use, water treatment (as oxygen kills some types of bacteria), rocket fuel (in liquid form), and metal cutting.

Most sulfur produced is transformed into sulfur dioxide, which is further transformed into sulfuric acid, a very common industrial chemical. Other common uses include being a key ingredient of gunpowder and Greek fire, and being used to change soil pH. Sulfur is also mixed into rubber to vulcanize it. Sulfur is used in some types of concrete and fireworks. 60% of all sulfuric acid produced is used to generate phosphoric acid. Sulfur is used as a pesticide (specifically as an acaricide and fungicide) on "orchard, ornamental, vegetable, grain, and other crops."

Around 40% of all selenium produced goes to glassmaking. 30% of all selenium produced goes to metallurgy, including manganese production. 15% of all selenium produced goes to agriculture. Electronics such as photovoltaic materials claim 10% of all selenium produced. Pigments account for 5% of all selenium produced. Historically, machines such as photocopiers and light meters used one-third of all selenium produced, but this application is in steady decline.

Tellurium suboxide, a mixture of tellurium and tellurium dioxide, is used in the rewritable data layer of some CD-RW disks and DVD-RW disks. Bismuth telluride is also used in many microelectronic devices, such as photoreceptors. Tellurium is sometimes used as an alternative to sulfur in vulcanized rubber. Cadmium telluride is used as a high-efficiency material in solar panels.

Some of polonium's applications relate to the element's radioactivity. For instance, polonium is used as an alpha-particle generator for research. Polonium alloyed with beryllium provides an efficient neutron source. Polonium is also used in nuclear batteries. Most polonium is used in antistatic devices. Livermorium does not have any uses whatsoever due to its extreme rarity and short half-life.

Organochalcogen compounds are involved in the semiconductor process. These compounds also feature into ligand chemistry and biochemistry. One application of chalcogens themselves is to manipulate redox couples in supramolecular chemistry (chemistry involving non-covalent bond interactions). This application leads on to such applications as crystal packing, assembly of large molecules, and biological recognition of patterns. The secondary bonding interactions of the larger chalcogens, selenium and tellurium, can create organic solvent-holding acetylene nanotubes. Chalcogen interactions are useful for conformational analysis and stereoelectronic effects, among other things. Chalcogenides with through bonds also have applications. For instance, divalent sulfur can stabilize carbanions, cationic centers, and radical. Chalcogens can confer upon ligands (such as DCTO) properties such as being able to transform Cu(II) to Cu(I). Studying chalcogen interactions gives access to radical cations, which are used in mainstream synthetic chemistry. Metallic redox centers of biological importance are tunable by interactions of ligands containing chalcogens, such as methionine and selenocysteine. Also, chalcogen through-bonds can provide insight about the process of electron transfer.

Biological role
Oxygen is needed by almost all organisms for the purpose of generating ATP. It is also a key component of most other biological compounds, such as water, amino acids and DNA. Human blood contains a large amount of oxygen. Human bones contain 28% oxygen. Human tissue contains 16% oxygen. A typical 70-kilogram human contains 43 kilograms of oxygen, mostly in the form of water.

All animals need significant amounts of sulfur. Some amino acids, such as cysteine and methionine contain sulfur. Plant roots take up sulfate ions from the soil and reduce it to sulfide ions. Metalloproteins also use sulfur to attach to useful metal atoms in the body and sulfur similarly attaches itself to poisonous metal atoms like cadmium to haul them to the safety of the liver. On average, humans consume 900 milligrams of sulfur each day. Sulfur compounds, such as those found in skunk spray often have strong odors.

All animals and some plants need trace amounts of selenium, but only for some specialized enzymes. Humans consume on average between 6 and 200 micrograms of selenium per day. Mushrooms and brazil nuts are especially noted for their high selenium content. Selenium in foods is most commonly found in the form of amino acids such as selenocysteine and selenomethionine. Selenium can protect against heavy metal poisoning.

Tellurium is not known to be needed for animal life, although a few fungi can incorporate it in compounds in place of selenium. Microorganisms also absorb tellurium and emit dimethyl telluride. Most tellurium in the blood stream is excreted slowly in urine, but some is converted to dimethyl telluride and released through the lungs. On average, humans ingest about 600 micrograms of tellurium daily. Plants can take up some tellurium from the soil. Onions and garlic have been found to contain as much as 300 parts per million of tellurium in dry weight.

Polonium has no biological role, and is highly toxic on account of being radioactive.

Toxicity
Oxygen is generally nontoxic, but oxygen toxicity has been reported when it is used in high concentrations. In both elemental gaseous form and as a component of water, it is vital to almost all life on Earth. Despite this, liquid oxygen is highly dangerous. Even gaseous oxygen is dangerous in excess. For instance, sports divers have occasionally drowned from convulsions caused by breathing pure oxygen at a depth of more than 10 m underwater. Oxygen is also toxic to some bacteria. Ozone, an allotrope of oxygen, is toxic to most life. It can cause lesions in the respiratory tract.

Sulfur is generally nontoxic and is even a vital nutrient for humans. However, in its elemental form it can cause redness in the eyes and skin, a burning sensation and a cough if inhaled, a burning sensation and diarrhoea and/or catharsis if ingested, and can irritate the mucous membranes. An excess of sulfur can be toxic for cows because microbes in the rumens of cows produce toxic hydrogen sulfide upon reaction with sulfur. Many sulfur compounds, such as hydrogen sulfide (H2S) and sulfur dioxide (SO2) are highly toxic.

Selenium is a trace nutrient required by humans on the order of tens or hundreds of micrograms per day. A dose of over 450 micrograms can be toxic, resulting in bad breath and body odor. Extended, low-level exposure, which can occur at some industries, results in weight loss, anemia, and dermatitis. In many cases of selenium poisoning, selenous acid is formed in the body. Hydrogen selenide (H2Se) is highly toxic.

Exposure to tellurium can produce unpleasant side effects. As little as 10 micrograms of tellurium per cubic meter of air can cause notoriously unpleasant breath, described as smelling like rotten garlic. Acute tellurium poisoning can cause vomiting, gut inflammation, internal bleeding, and respiratory failure. Extended, low-level exposure to tellurium causes tiredness and indigestion. Sodium tellurite (Na2TeO3) is lethal in amounts of around 2 grams.

Polonium is dangerous as an alpha particle emitter. If ingested, polonium-210 is a million times as toxic as hydrogen cyanide by weight; it has been used as a murder weapon in the past, most famously to kill Alexander Litvinenko. Polonium poisoning can cause nausea, vomiting, anorexia, and lymphopenia. It can also damage hair follicles and white blood cells. Polonium-210 is only dangerous if ingested or inhaled because its alpha particle emissions cannot penetrate human skin. Polonium-209 is also toxic, and can cause leukemia.

Amphid salts
Amphid salts was a name given by Jons Jacob Berzelius in the 19th century for chemical salts derived from the 16th group of the periodic table which included oxygen, sulfur, selenium, and tellurium. The term received some use in the early 1800s but is now obsolete. The current term in use for the 16th group is chalcogens.

title: Chalcogen


text:
Carbon dioxide

Carbon dioxide is a chemical compound with the chemical formula CO2. It is made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature, and as the source of available carbon in the carbon cycle, atmospheric is the primary carbon source for life on Earth. In the air, carbon dioxide is transparent to visible light but absorbs infrared radiation, acting as a greenhouse gas. Carbon dioxide is soluble in water and is found in groundwater, lakes, ice caps, and seawater. When carbon dioxide dissolves in water, it forms carbonate and mainly bicarbonate (HCO3-), which causes ocean acidification as atmospheric levels increase.

It is a trace gas in Earth's atmosphere at 421 parts per million (ppm), or about 0.04% (as of May 2022) having risen from pre-industrial levels of 280 ppm or about 0.025%. Burning fossil fuels is the primary cause of these increased concentrations and also the primary cause of climate change.

Its concentration in Earth's pre-industrial atmosphere since late in the Precambrian was regulated by organisms and geological phenomena. Plants, algae and cyanobacteria use energy from sunlight to synthesize carbohydrates from carbon dioxide and water in a process called photosynthesis, which produces oxygen as a waste product. In turn, oxygen is consumed and is released as waste by all aerobic organisms when they metabolize organic compounds to produce energy by respiration. is released from organic materials when they decay or combust, such as in forest fires.

Carbon dioxide is 53% more dense than dry air, but is long lived and thoroughly mixes in the atmosphere. About half of excess emissions to the atmosphere are absorbed by land and ocean carbon sinks. These sinks can become saturated and are volatile, as decay and wildfires result in the being released back into the atmosphere. is eventually sequestered (stored for the long term) in rocks and organic deposits like coal, petroleum and natural gas. Sequestered is released into the atmosphere through burning fossil fuels or naturally by volcanoes, hot springs, geysers, and when carbonate rocks dissolve in water or react with acids.

is a versatile industrial material, used, for example, as an inert gas in welding and fire extinguishers, as a pressurizing gas in air guns and oil recovery, and as a supercritical fluid solvent in decaffeination and supercritical drying. It is a byproduct of fermentation of sugars in bread, beer and wine making, and is added to carbonated beverages like seltzer and beer for effervescence. It has a sharp and acidic odor and generates the taste of soda water in the mouth, but at normally encountered concentrations it is odorless.

Chemical and physical properties
Carbon dioxide cannot be liquefied at atmospheric pressure. Low-temperature carbon dioxide is commercially used in its solid form, commonly known as "dry ice". The solid-to-gas phase transition occurs at 194.7 Kelvin and is called sublimation.

Structure, bonding and molecular vibrations
The symmetry of a carbon dioxide molecule is linear and centrosymmetric at its equilibrium geometry. The length of the carbon–oxygen bond in carbon dioxide is 116.3 pm, noticeably shorter than the roughly 140 pm length of a typical single C–O bond, and shorter than most other C–O multiply bonded functional groups such as carbonyls. Since it is centrosymmetric, the molecule has no electric dipole moment.

As a linear triatomic molecule, has four vibrational modes as shown in the diagram. In the symmetric and the antisymmetric stretching modes, the atoms move along the axis of the molecule. There are two bending modes, which are degenerate, meaning that they have the same frequency and same energy, because of the symmetry of the molecule. When a molecule touches a surface or touches another molecule, the two bending modes can differ in frequency because the interaction is different for the two modes. Some of the vibrational modes are observed in the infrared (IR) spectrum: the antisymmetric stretching mode at wavenumber 2349 cm−1 (wavelength 4.25 μm) and the degenerate pair of bending modes at 667 cm−1 (wavelength 15 μm). The symmetric stretching mode does not create an electric dipole so is not observed in IR spectroscopy, but it is detected in Raman spectroscopy at 1388 cm−1 (wavelength 7.2 μm).

In the gas phase, carbon dioxide molecules undergo significant vibrational motions and do not keep a fixed structure. However, in a Coulomb explosion imaging experiment, an instantaneous image of the molecular structure can be deduced. Such an experiment has been performed for carbon dioxide. The result of this experiment, and the conclusion of theoretical calculations based on an ab initio potential energy surface of the molecule, is that none of the molecules in the gas phase are ever exactly linear. This counter-intuitive result is trivially due to the fact that the nuclear motion volume element vanishes for linear geometries. This is so for all molecules except diatomic molecules.

In aqueous solution
Carbon dioxide is soluble in water, in which it reversibly forms H2CO3 (carbonic acid), which is a weak acid, because its ionization in water is incomplete.
 * CO2 + H2O ⇌ H2CO3

The hydration equilibrium constant of carbonic acid is, at 25 °C:

Hence, the majority of the carbon dioxide is not converted into carbonic acid, but remains as molecules, not affecting the pH.

The relative concentrations of, H2CO3, and the deprotonated forms HCO3- (bicarbonate) and CO3(2-)(carbonate) depend on the pH. As shown in a Bjerrum plot, in neutral or slightly alkaline water (pH > 6.5), the bicarbonate form predominates (>50%) becoming the most prevalent (>95%) at the pH of seawater. In very alkaline water (pH > 10.4), the predominant (>50%) form is carbonate. The oceans, being mildly alkaline with typical pH = 8.2–8.5, contain about 120 mg of bicarbonate per liter.

Being diprotic, carbonic acid has two acid dissociation constants, the first one for the dissociation into the bicarbonate (also called hydrogen carbonate) ion (HCO3-):

 * H2CO3 ⇌ HCO3- + H+
 * Ka1 = 2.5 × 10−4 mol/L; pKa1 = 3.6 at 25 °C.

This is the true first acid dissociation constant, defined as

where the denominator includes only covalently bound H2CO3 and does not include hydrated (aq). The much smaller and often-quoted value near 4.16 × 10−7 (or pKa1 = 6.38) is an apparent value calculated on the (incorrect) assumption that all dissolved is present as carbonic acid, so that

Since most of the dissolved remains as  molecules, Ka1(apparent) has a much larger denominator and a much smaller value than the true Ka1.

The bicarbonate ion is an amphoteric species that can act as an acid or as a base, depending on pH of the solution. At high pH, it dissociates significantly into the carbonate ion (CO3(2-)):
 * HCO3- ⇌ CO3(2-) + H+
 * Ka2 = 4.69 × 10−11 mol/L; pKa2 = 10.329

In organisms, carbonic acid production is catalysed by the enzyme known as carbonic anhydrase.

In addition to altering its acidity, the presence of carbon dioxide in water also affects its electrical properties. When carbon dioxide dissolves in desalinated water, the electrical conductivity increases significantly from below 1 μS/cm to nearly 30 μS/cm. When heated, the water begins to gradually lose the conductivity induced by the presence of $$ \mathrm{CO_{2}} $$, especially noticeable as temperatures exceed 30 °C.

The temperature dependence of the electrical conductivity of fully deionized water without $$\mathrm{CO_{2}} $$ saturation is comparably low in relation to these data.

Chemical reactions
is a potent electrophile having an electrophilic reactivity that is comparable to benzaldehyde or strongly electrophilic α,β-unsaturated carbonyl compounds. However, unlike electrophiles of similar reactivity, the reactions of nucleophiles with are thermodynamically less favored and are often found to be highly reversible. The reversible reaction of carbon dioxide with amines to make carbamates is used in scrubbers and has been suggested as a possible starting point for carbon capture and storage by amine gas treating. Only very strong nucleophiles, like the carbanions provided by Grignard reagents and organolithium compounds react with to give carboxylates:
 * MR + CO2 → RCO2M
 * where M = Li or MgBr and R = alkyl or aryl.

In metal carbon dioxide complexes, serves as a ligand, which can facilitate the conversion of  to other chemicals.

The reduction of to CO is ordinarily a difficult and slow reaction:
 * CO2 + 2 e- + 2 H+ → CO + H2O

The redox potential for this reaction near pH 7 is about −0.53 V versus the standard hydrogen electrode. The nickel-containing enzyme carbon monoxide dehydrogenase catalyses this process.

Photoautotrophs (i.e. plants and cyanobacteria) use the energy contained in sunlight to photosynthesize simple sugars from absorbed from the air and water:
 * n CO2 + n H2O → (CH2O)_{n} + n O2

Physical properties
Carbon dioxide is colorless. At low concentrations, the gas is odorless; however, at sufficiently high concentrations, it has a sharp, acidic odor. At standard temperature and pressure, the density of carbon dioxide is around 1.98 kg/m3, about 1.53 times that of air.

Carbon dioxide has no liquid state at pressures below 0.51795(10) MPa (5.11177(99) atm). At a pressure of 1 atm (0.101325 MPa), the gas deposits directly to a solid at temperatures below 194.6855(30) K (−78.4645(30) °C) and the solid sublimes directly to a gas above this temperature. In its solid state, carbon dioxide is commonly called dry ice.

Liquid carbon dioxide forms only at pressures above 0.51795(10) MPa (5.11177(99) atm); the triple point of carbon dioxide is 216.592(3) K (−56.558(3) °C) at 0.51795(10) MPa (5.11177(99) atm) (see phase diagram). The critical point is 304.128(15) K (30.978(15) °C) at 7.3773(30) MPa (72.808(30) atm). Another form of solid carbon dioxide observed at high pressure is an amorphous glass-like solid. This form of glass, called carbonia, is produced by supercooling heated at extreme pressures (40–48 GPa, or about 400,000 atmospheres) in a diamond anvil. This discovery confirmed the theory that carbon dioxide could exist in a glass state similar to other members of its elemental family, like silicon dioxide (silica glass) and germanium dioxide. Unlike silica and germania glasses, however, carbonia glass is not stable at normal pressures and reverts to gas when pressure is released.

At temperatures and pressures above the critical point, carbon dioxide behaves as a supercritical fluid known as supercritical carbon dioxide.

Table of thermal and physical properties of saturated liquid carbon dioxide: Table of thermal and physical properties of carbon dioxide at atmospheric pressure:

Biological role
Carbon dioxide is an end product of cellular respiration in organisms that obtain energy by breaking down sugars, fats and amino acids with oxygen as part of their metabolism. This includes all plants, algae and animals and aerobic fungi and bacteria. In vertebrates, the carbon dioxide travels in the blood from the body's tissues to the skin (e.g., amphibians) or the gills (e.g., fish), from where it dissolves in the water, or to the lungs from where it is exhaled. During active photosynthesis, plants can absorb more carbon dioxide from the atmosphere than they release in respiration.

Photosynthesis and carbon fixation
Carbon fixation is a biochemical process by which atmospheric carbon dioxide is incorporated by plants, algae and cyanobacteria into energy-rich organic molecules such as glucose, thus creating their own food by photosynthesis. Photosynthesis uses carbon dioxide and water to produce sugars from which other organic compounds can be constructed, and oxygen is produced as a by-product.

Ribulose-1,5-bisphosphate carboxylase oxygenase, commonly abbreviated to RuBisCO, is the enzyme involved in the first major step of carbon fixation, the production of two molecules of 3-phosphoglycerate from and ribulose bisphosphate, as shown in the diagram at left.

RuBisCO is thought to be the single most abundant protein on Earth.

Phototrophs use the products of their photosynthesis as internal food sources and as raw material for the biosynthesis of more complex organic molecules, such as polysaccharides, nucleic acids, and proteins. These are used for their own growth, and also as the basis of the food chains and webs that feed other organisms, including animals such as ourselves. Some important phototrophs, the coccolithophores synthesise hard calcium carbonate scales. A globally significant species of coccolithophore is Emiliania huxleyi whose calcite scales have formed the basis of many sedimentary rocks such as limestone, where what was previously atmospheric carbon can remain fixed for geological timescales.

Plants can grow as much as 50% faster in concentrations of 1,000 ppm when compared with ambient conditions, though this assumes no change in climate and no limitation on other nutrients. Elevated levels cause increased growth reflected in the harvestable yield of crops, with wheat, rice and soybean all showing increases in yield of 12–14% under elevated  in FACE experiments.

Increased atmospheric concentrations result in fewer stomata developing on plants which leads to reduced water usage and increased water-use efficiency. Studies using FACE have shown that enrichment leads to decreased concentrations of micronutrients in crop plants. This may have knock-on effects on other parts of ecosystems as herbivores will need to eat more food to gain the same amount of protein.

The concentration of secondary metabolites such as phenylpropanoids and flavonoids can also be altered in plants exposed to high concentrations of.

Plants also emit during respiration, and so the majority of plants and algae, which use C3 photosynthesis, are only net absorbers during the day. Though a growing forest will absorb many tons of each year, a mature forest will produce as much  from respiration and decomposition of dead specimens (e.g., fallen branches) as is used in photosynthesis in growing plants. Contrary to the long-standing view that they are carbon neutral, mature forests can continue to accumulate carbon and remain valuable carbon sinks, helping to maintain the carbon balance of Earth's atmosphere. Additionally, and crucially to life on earth, photosynthesis by phytoplankton consumes dissolved in the upper ocean and thereby promotes the absorption of  from the atmosphere.

Toxicity

Carbon dioxide content in fresh air (averaged between sea-level and 10 kPa level, i.e., about 30 km altitude) varies between 0.036% (360 ppm) and 0.041% (412 ppm), depending on the location.

is an asphyxiant gas and not classified as toxic or harmful in accordance with Globally Harmonized System of Classification and Labelling of Chemicals standards of United Nations Economic Commission for Europe by using the OECD Guidelines for the Testing of Chemicals. In concentrations up to 1% (10,000 ppm), it will make some people feel drowsy and give the lungs a stuffy feeling. Concentrations of 7% to 10% (70,000 to 100,000 ppm) may cause suffocation, even in the presence of sufficient oxygen, manifesting as dizziness, headache, visual and hearing dysfunction, and unconsciousness within a few minutes to an hour. The physiological effects of acute carbon dioxide exposure are grouped together under the term hypercapnia, a subset of asphyxiation.

Because it is heavier than air, in locations where the gas seeps from the ground (due to sub-surface volcanic or geothermal activity) in relatively high concentrations, without the dispersing effects of wind, it can collect in sheltered/pocketed locations below average ground level, causing animals located therein to be suffocated. Carrion feeders attracted to the carcasses are then also killed. Children have been killed in the same way near the city of Goma by emissions from the nearby volcano Mount Nyiragongo. The Swahili term for this phenomenon is mazuku.

Adaptation to increased concentrations of occurs in humans, including modified breathing and kidney bicarbonate production, in order to balance the effects of blood acidification (acidosis). Several studies suggested that 2.0 percent inspired concentrations could be used for closed air spaces (e.g. a submarine) since the adaptation is physiological and reversible, as deterioration in performance or in normal physical activity does not happen at this level of exposure for five days. Yet, other studies show a decrease in cognitive function even at much lower levels. Also, with ongoing respiratory acidosis, adaptation or compensatory mechanisms will be unable to reverse the condition.

Below 1%
There are few studies of the health effects of long-term continuous exposure on humans and animals at levels below 1%. Occupational exposure limits have been set in the United States at 0.5% (5000 ppm) for an eight-hour period. At this concentration, International Space Station crew experienced headaches, lethargy, mental slowness, emotional irritation, and sleep disruption. Studies in animals at 0.5% have demonstrated kidney calcification and bone loss after eight weeks of exposure. A study of humans exposed in 2.5 hour sessions demonstrated significant negative effects on cognitive abilities at concentrations as low as 0.1% (1000ppm) likely due to  induced increases in cerebral blood flow. Another study observed a decline in basic activity level and information usage at 1000 ppm, when compared to 500 ppm.

However a review of the literature found that a reliable subset of studies on the phenomenon of carbon dioxide induced cognitive impairment to only show a small effect on high-level decision making (for concentrations below 5000 ppm). Most of the studies were confounded by inadequate study designs, environmental comfort, uncertainties in exposure doses and differing cognitive assessments used. Similarly a study on the effects of the concentration of in motorcycle helmets has been criticized for having dubious methodology in not noting the self-reports of motorcycle riders and taking measurements using mannequins. Further when normal motorcycle conditions were achieved (such as highway or city speeds) or the visor was raised the concentration of declined to safe levels (0.2%).

Ventilation
Poor ventilation is one of the main causes of excessive concentrations in closed spaces, leading to poor indoor air quality. Carbon dioxide differential above outdoor concentrations at steady state conditions (when the occupancy and ventilation system operation are sufficiently long that concentration has stabilized) are sometimes used to estimate ventilation rates per person. Higher concentrations are associated with occupant health, comfort and performance degradation. ASHRAE Standard 62.1–2007 ventilation rates may result in indoor concentrations up to 2,100 ppm above ambient outdoor conditions. Thus if the outdoor concentration is 400 ppm, indoor concentrations may reach 2,500 ppm with ventilation rates that meet this industry consensus standard. Concentrations in poorly ventilated spaces can be found even higher than this (range of 3,000 or 4,000 ppm).

Miners, who are particularly vulnerable to gas exposure due to insufficient ventilation, referred to mixtures of carbon dioxide and nitrogen as "blackdamp", "choke damp" or "stythe". Before more effective technologies were developed, miners would frequently monitor for dangerous levels of blackdamp and other gases in mine shafts by bringing a caged canary with them as they worked. The canary is more sensitive to asphyxiant gases than humans, and as it became unconscious would stop singing and fall off its perch. The Davy lamp could also detect high levels of blackdamp (which sinks, and collects near the floor) by burning less brightly, while methane, another suffocating gas and explosion risk, would make the lamp burn more brightly.

In February 2020, three people died from suffocation at a party in Moscow when dry ice (frozen ) was added to a swimming pool to cool it down. A similar accident occurred in 2018 when a woman died from fumes emanating from the large amount of dry ice she was transporting in her car.

Indoor air
Humans spend more and more time in a confined atmosphere (around 80-90% of the time in a building or vehicle). According to the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) and various actors in France, the rate in the indoor air of buildings (linked to human or animal occupancy and the presence of combustion installations), weighted by air renewal, is "usually between about 350 and 2,500 ppm".

In homes, schools, nurseries and offices, there are no systematic relationships between the levels of and other pollutants, and indoor  is statistically not a good predictor of pollutants linked to outdoor road (or air, etc.) traffic. is the parameter that changes the fastest (with hygrometry and oxygen levels when humans or animals are gathered in a closed or poorly ventilated room). In poor countries, many open hearths are sources of and CO emitted directly into the living environment.

Outdoor areas with elevated concentrations
Local concentrations of carbon dioxide can reach high values near strong sources, especially those that are isolated by surrounding terrain. At the Bossoleto hot spring near Rapolano Terme in Tuscany, Italy, situated in a bowl-shaped depression about 100 m in diameter, concentrations of rise to above 75% overnight, sufficient to kill insects and small animals. After sunrise the gas is dispersed by convection. High concentrations of produced by disturbance of deep lake water saturated with  are thought to have caused 37 fatalities at Lake Monoun, Cameroon in 1984 and 1700 casualties at Lake Nyos, Cameroon in 1986.

Content
The body produces approximately 2.3 lb of carbon dioxide per day per person, containing 0.63 lb of carbon. In humans, this carbon dioxide is carried through the venous system and is breathed out through the lungs, resulting in lower concentrations in the arteries. The carbon dioxide content of the blood is often given as the partial pressure, which is the pressure which carbon dioxide would have had if it alone occupied the volume. In humans, the blood carbon dioxide contents are shown in the adjacent table.

Transport in the blood
is carried in blood in three different ways. Exact percentages vary between arterial and venous blood.
 * Majority (about 70% to 80%) is converted to bicarbonate ions HCO3- by the enzyme carbonic anhydrase in the red blood cells, by the reaction:
 * CO2 + H2O → H2CO3 → H+ + HCO3-

 * 5–10% is dissolved in blood plasma
 * 5–10% is bound to hemoglobin as carbamino compounds

Hemoglobin, the main oxygen-carrying molecule in red blood cells, carries both oxygen and carbon dioxide. However, the bound to hemoglobin does not bind to the same site as oxygen. Instead, it combines with the N-terminal groups on the four globin chains. However, because of allosteric effects on the hemoglobin molecule, the binding of decreases the amount of oxygen that is bound for a given partial pressure of oxygen. This is known as the Haldane Effect, and is important in the transport of carbon dioxide from the tissues to the lungs. Conversely, a rise in the partial pressure of or a lower pH will cause offloading of oxygen from hemoglobin, which is known as the Bohr effect.

Regulation of respiration
Carbon dioxide is one of the mediators of local autoregulation of blood supply. If its concentration is high, the capillaries expand to allow a greater blood flow to that tissue.

Bicarbonate ions are crucial for regulating blood pH. A person's breathing rate influences the level of in their blood. Breathing that is too slow or shallow causes respiratory acidosis, while breathing that is too rapid leads to hyperventilation, which can cause respiratory alkalosis.

Although the body requires oxygen for metabolism, low oxygen levels normally do not stimulate breathing. Rather, breathing is stimulated by higher carbon dioxide levels. As a result, breathing low-pressure air or a gas mixture with no oxygen at all (such as pure nitrogen) can lead to loss of consciousness without ever experiencing air hunger. This is especially perilous for high-altitude fighter pilots. It is also why flight attendants instruct passengers, in case of loss of cabin pressure, to apply the oxygen mask to themselves first before helping others; otherwise, one risks losing consciousness.

The respiratory centers try to maintain an arterial pressure of 40 mmHg. With intentional hyperventilation, the content of arterial blood may be lowered to 10–20 mmHg (the oxygen content of the blood is little affected), and the respiratory drive is diminished. This is why one can hold one's breath longer after hyperventilating than without hyperventilating. This carries the risk that unconsciousness may result before the need to breathe becomes overwhelming, which is why hyperventilation is particularly dangerous before free diving.

Ocean acidification
Carbon dioxide dissolves in the ocean to form carbonic acid (H2CO3), bicarbonate (HCO3-), and carbonate (CO3(2-)). There is about fifty times as much carbon dioxide dissolved in the oceans as exists in the atmosphere. The oceans act as an enormous carbon sink, and have taken up about a third of emitted by human activity.

Hydrothermal vents
Carbon dioxide is also introduced into the oceans through hydrothermal vents. The Champagne hydrothermal vent, found at the Northwest Eifuku volcano in the Mariana Trench, produces almost pure liquid carbon dioxide, one of only two known sites in the world as of 2004, the other being in the Okinawa Trough. The finding of a submarine lake of liquid carbon dioxide in the Okinawa Trough was reported in 2006.

Biological processes
Carbon dioxide is a by-product of the fermentation of sugar in the brewing of beer, whisky and other alcoholic beverages and in the production of bioethanol. Yeast metabolizes sugar to produce and ethanol, also known as alcohol, as follows:
 * C6H12O6 → 2 CO2 + 2 CH3CH2OH

All aerobic organisms produce when they oxidize carbohydrates, fatty acids, and proteins. The large number of reactions involved are exceedingly complex and not described easily. Refer to cellular respiration, anaerobic respiration and photosynthesis. The equation for the respiration of glucose and other monosaccharides is:
 * C6H12O6 + 6 O2 → 6 CO2 + 6 H2O

Anaerobic organisms decompose organic material producing methane and carbon dioxide together with traces of other compounds. Regardless of the type of organic material, the production of gases follows well defined kinetic pattern. Carbon dioxide comprises about 40–45% of the gas that emanates from decomposition in landfills (termed "landfill gas"). Most of the remaining 50–55% is methane.

Industrial processes
Carbon dioxide can be obtained by distillation from air, but the method is inefficient. Industrially, carbon dioxide is predominantly an unrecovered waste product, produced by several methods which may be practiced at various scales.

Combustion
The combustion of all carbon-based fuels, such as methane (natural gas), petroleum distillates (gasoline, diesel, kerosene, propane), coal, wood and generic organic matter produces carbon dioxide and, except in the case of pure carbon, water. As an example, the chemical reaction between methane and oxygen:
 * CH4 + 2 O2 → CO2 + 2 H2O

Iron is reduced from its oxides with coke in a blast furnace, producing pig iron and carbon dioxide:
 * Fe2O3 + 3 CO → 3 CO2 + 2 Fe

By-product from hydrogen production
Carbon dioxide is a byproduct of the industrial production of hydrogen by steam reforming and the water gas shift reaction in ammonia production. These processes begin with the reaction of water and natural gas (mainly methane). This is a major source of food-grade carbon dioxide for use in carbonation of beer and soft drinks, and is also used for stunning animals such as poultry. In the summer of 2018 a shortage of carbon dioxide for these purposes arose in Europe due to the temporary shut-down of several ammonia plants for maintenance.

Thermal decomposition of limestone
It is produced by thermal decomposition of limestone, CaCO3 by heating (calcining) at about 850 C, in the manufacture of quicklime (calcium oxide, CaO), a compound that has many industrial uses:
 * CaCO3 → CaO + CO2

Acids liberate from most metal carbonates. Consequently, it may be obtained directly from natural carbon dioxide springs, where it is produced by the action of acidified water on limestone or dolomite. The reaction between hydrochloric acid and calcium carbonate (limestone or chalk) is shown below:
 * CaCO3 + 2 HCl → CaCl2 + H2CO3

The carbonic acid (H2CO3) then decomposes to water and :
 * H2CO3 → CO2 + H2O

Such reactions are accompanied by foaming or bubbling, or both, as the gas is released. They have widespread uses in industry because they can be used to neutralize waste acid streams.

Commercial uses
Carbon dioxide is used by the food industry, the oil industry, and the chemical industry. The compound has varied commercial uses but one of its greatest uses as a chemical is in the production of carbonated beverages; it provides the sparkle in carbonated beverages such as soda water, beer and sparkling wine.

Precursor to chemicals
In the chemical industry, carbon dioxide is mainly consumed as an ingredient in the production of urea, with a smaller fraction being used to produce methanol and a range of other products. Some carboxylic acid derivatives such as sodium salicylate are prepared using by the Kolbe–Schmitt reaction.

In addition to conventional processes using for chemical production, electrochemical methods are also being explored at a research level. In particular, the use of renewable energy for production of fuels from (such as methanol) is attractive as this could result in fuels that could be easily transported and used within conventional combustion technologies but have no net  emissions.

Agriculture
Plants require carbon dioxide to conduct photosynthesis. The atmospheres of greenhouses may (if of large size, must) be enriched with additional to sustain and increase the rate of plant growth. At very high concentrations (100 times atmospheric concentration, or greater), carbon dioxide can be toxic to animal life, so raising the concentration to 10,000 ppm (1%) or higher for several hours will eliminate pests such as whiteflies and spider mites in a greenhouse. Some plants respond more favorably to rising carbon dioxide concentrations than others, which can lead to vegetation regime shifts like woody plant encroachment.

Foods

Carbon dioxide is a food additive used as a propellant and acidity regulator in the food industry. It is approved for usage in the EU (listed as E number E290), US, Australia and New Zealand (listed by its INS number 290).

A candy called Pop Rocks is pressurized with carbon dioxide gas at about 4000 kPa. When placed in the mouth, it dissolves (just like other hard candy) and releases the gas bubbles with an audible pop.

Leavening agents cause dough to rise by producing carbon dioxide. Baker's yeast produces carbon dioxide by fermentation of sugars within the dough, while chemical leaveners such as baking powder and baking soda release carbon dioxide when heated or if exposed to acids.

Beverages
Carbon dioxide is used to produce carbonated soft drinks and soda water. Traditionally, the carbonation of beer and sparkling wine came about through natural fermentation, but many manufacturers carbonate these drinks with carbon dioxide recovered from the fermentation process. In the case of bottled and kegged beer, the most common method used is carbonation with recycled carbon dioxide. With the exception of British real ale, draught beer is usually transferred from kegs in a cold room or cellar to dispensing taps on the bar using pressurized carbon dioxide, sometimes mixed with nitrogen.

The taste of soda water (and related taste sensations in other carbonated beverages) is an effect of the dissolved carbon dioxide rather than the bursting bubbles of the gas. Carbonic anhydrase 4 converts carbon dioxide to carbonic acid leading to a sour taste, and also the dissolved carbon dioxide induces a somatosensory response.

Winemaking
Carbon dioxide in the form of dry ice is often used during the cold soak phase in winemaking to cool clusters of grapes quickly after picking to help prevent spontaneous fermentation by wild yeast. The main advantage of using dry ice over water ice is that it cools the grapes without adding any additional water that might decrease the sugar concentration in the grape must, and thus the alcohol concentration in the finished wine. Carbon dioxide is also used to create a hypoxic environment for carbonic maceration, the process used to produce Beaujolais wine.

Carbon dioxide is sometimes used to top up wine bottles or other storage vessels such as barrels to prevent oxidation, though it has the problem that it can dissolve into the wine, making a previously still wine slightly fizzy. For this reason, other gases such as nitrogen or argon are preferred for this process by professional wine makers.

Stunning animals
Carbon dioxide is often used to "stun" animals before slaughter. "Stunning" may be a misnomer, as the animals are not knocked out immediately and may suffer distress.

Inert gas
Carbon dioxide is one of the most commonly used compressed gases for pneumatic (pressurized gas) systems in portable pressure tools. Carbon dioxide is also used as an atmosphere for welding, although in the welding arc, it reacts to oxidize most metals. Use in the automotive industry is common despite significant evidence that welds made in carbon dioxide are more brittle than those made in more inert atmospheres. When used for MIG welding, use is sometimes referred to as MAG welding, for Metal Active Gas, as  can react at these high temperatures. It tends to produce a hotter puddle than truly inert atmospheres, improving the flow characteristics. Although, this may be due to atmospheric reactions occurring at the puddle site. This is usually the opposite of the desired effect when welding, as it tends to embrittle the site, but may not be a problem for general mild steel welding, where ultimate ductility is not a major concern.

Carbon dioxide is used in many consumer products that require pressurized gas because it is inexpensive and nonflammable, and because it undergoes a phase transition from gas to liquid at room temperature at an attainable pressure of approximately 60 bar, allowing far more carbon dioxide to fit in a given container than otherwise would. Life jackets often contain canisters of pressured carbon dioxide for quick inflation. Aluminium capsules of are also sold as supplies of compressed gas for air guns, paintball markers/guns, inflating bicycle tires, and for making carbonated water. High concentrations of carbon dioxide can also be used to kill pests. Liquid carbon dioxide is used in supercritical drying of some food products and technological materials, in the preparation of specimens for scanning electron microscopy and in the decaffeination of coffee beans.

Fire extinguisher
Carbon dioxide can be used to extinguish flames by flooding the environment around the flame with the gas. It does not itself react to extinguish the flame, but starves the flame of oxygen by displacing it. Some fire extinguishers, especially those designed for electrical fires, contain liquid carbon dioxide under pressure. Carbon dioxide extinguishers work well on small flammable liquid and electrical fires, but not on ordinary combustible fires, because they do not cool the burning substances significantly, and when the carbon dioxide disperses, they can catch fire upon exposure to atmospheric oxygen. They are mainly used in server rooms.

Carbon dioxide has also been widely used as an extinguishing agent in fixed fire-protection systems for local application of specific hazards and total flooding of a protected space. International Maritime Organization standards recognize carbon dioxide systems for fire protection of ship holds and engine rooms. Carbon dioxide-based fire-protection systems have been linked to several deaths, because it can cause suffocation in sufficiently high concentrations. A review of systems identified 51 incidents between 1975 and the date of the report (2000), causing 72 deaths and 145 injuries.

Supercritical as solvent
Liquid carbon dioxide is a good solvent for many lipophilic organic compounds and is used to decaffeinate coffee. Carbon dioxide has attracted attention in the pharmaceutical and other chemical processing industries as a less toxic alternative to more traditional solvents such as organochlorides. It is also used by some dry cleaners for this reason. It is used in the preparation of some aerogels because of the properties of supercritical carbon dioxide.

Medical and pharmacological uses
In medicine, up to 5% carbon dioxide (130 times atmospheric concentration) is added to oxygen for stimulation of breathing after apnea and to stabilize the O2/ balance in blood.

Carbon dioxide can be mixed with up to 50% oxygen, forming an inhalable gas; this is known as Carbogen and has a variety of medical and research uses.

Another medical use are the mofette, dry spas that use carbon dioxide from post-volcanic discharge for therapeutic purposes.

Energy
Supercritical is used as the working fluid in the Allam power cycle engine.

Fossil fuel recovery
Carbon dioxide is used in enhanced oil recovery where it is injected into or adjacent to producing oil wells, usually under supercritical conditions, when it becomes miscible with the oil. This approach can increase original oil recovery by reducing residual oil saturation by 7–23% additional to primary extraction. It acts as both a pressurizing agent and, when dissolved into the underground crude oil, significantly reduces its viscosity, and changing surface chemistry enabling the oil to flow more rapidly through the reservoir to the removal well. In mature oil fields, extensive pipe networks are used to carry the carbon dioxide to the injection points.

In enhanced coal bed methane recovery, carbon dioxide would be pumped into the coal seam to displace methane, as opposed to current methods which primarily rely on the removal of water (to reduce pressure) to make the coal seam release its trapped methane.

Bio transformation into fuel
It has been proposed that from power generation be bubbled into ponds to stimulate growth of algae that could then be converted into biodiesel fuel. A strain of the cyanobacterium Synechococcus elongatus has been genetically engineered to produce the fuels isobutyraldehyde and isobutanol from using photosynthesis.

Researchers have developed an electrocatalytic technique using enzymes isolated from bacteria to power the chemical reactions which convert into fuels.

Refrigerant

Liquid and solid carbon dioxide are important refrigerants, especially in the food industry, where they are employed during the transportation and storage of ice cream and other frozen foods. Solid carbon dioxide is called "dry ice" and is used for small shipments where refrigeration equipment is not practical. Solid carbon dioxide is always below -78.5 C at regular atmospheric pressure, regardless of the air temperature.

Liquid carbon dioxide (industry nomenclature R744 or R-744) was used as a refrigerant prior to the use of dichlorodifluoromethane (R12, a chlorofluorocarbon (CFC) compound). might enjoy a renaissance because one of the main substitutes to CFCs, 1,1,1,2-tetrafluoroethane (R134a, a hydrofluorocarbon (HFC) compound) contributes to climate change more than does. physical properties are highly favorable for cooling, refrigeration, and heating purposes, having a high volumetric cooling capacity. Due to the need to operate at pressures of up to 130 bar, systems require highly mechanically resistant reservoirs and components that have already been developed for mass production in many sectors. In automobile air conditioning, in more than 90% of all driving conditions for latitudes higher than 50°, (R744) operates more efficiently than systems using HFCs (e.g., R134a). Its environmental advantages (GWP of 1, non-ozone depleting, non-toxic, non-flammable) could make it the future working fluid to replace current HFCs in cars, supermarkets, and heat pump water heaters, among others. Coca-Cola has fielded -based beverage coolers and the U.S. Army is interested in refrigeration and heating technology.

Minor uses
Carbon dioxide is the lasing medium in a carbon-dioxide laser, which is one of the earliest type of lasers.

Carbon dioxide can be used as a means of controlling the pH of swimming pools, by continuously adding gas to the water, thus keeping the pH from rising. Among the advantages of this is the avoidance of handling (more hazardous) acids. Similarly, it is also used in the maintaining reef aquaria, where it is commonly used in calcium reactors to temporarily lower the pH of water being passed over calcium carbonate in order to allow the calcium carbonate to dissolve into the water more freely, where it is used by some corals to build their skeleton.

Used as the primary coolant in the British advanced gas-cooled reactor for nuclear power generation.

Carbon dioxide induction is commonly used for the euthanasia of laboratory research animals. Methods to administer include placing animals directly into a closed, prefilled chamber containing, or exposure to a gradually increasing concentration of. The American Veterinary Medical Association's 2020 guidelines for carbon dioxide induction state that a displacement rate of 30–70% of the chamber or cage volume per minute is optimal for the humane euthanasia of small rodents. Percentages of vary for different species, based on identified optimal percentages to minimize distress.

Carbon dioxide is also used in several related cleaning and surface-preparation techniques.

History of discovery
Carbon dioxide was the first gas to be described as a discrete substance. In about 1640, the Flemish chemist Jan Baptist van Helmont observed that when he burned charcoal in a closed vessel, the mass of the resulting ash was much less than that of the original charcoal. His interpretation was that the rest of the charcoal had been transmuted into an invisible substance he termed a "gas" (from Greek "chaos") or "wild spirit" (spiritus sylvestris).

The properties of carbon dioxide were further studied in the 1750s by the Scottish physician Joseph Black. He found that limestone (calcium carbonate) could be heated or treated with acids to yield a gas he called "fixed air". He observed that the fixed air was denser than air and supported neither flame nor animal life. Black also found that when bubbled through limewater (a saturated aqueous solution of calcium hydroxide), it would precipitate calcium carbonate. He used this phenomenon to illustrate that carbon dioxide is produced by animal respiration and microbial fermentation. In 1772, English chemist Joseph Priestley published a paper entitled Impregnating Water with Fixed Air in which he described a process of dripping sulfuric acid (or oil of vitriol as Priestley knew it) on chalk in order to produce carbon dioxide, and forcing the gas to dissolve by agitating a bowl of water in contact with the gas.

Carbon dioxide was first liquefied (at elevated pressures) in 1823 by Humphry Davy and Michael Faraday. The earliest description of solid carbon dioxide (dry ice) was given by the French inventor Adrien-Jean-Pierre Thilorier, who in 1835 opened a pressurized container of liquid carbon dioxide, only to find that the cooling produced by the rapid evaporation of the liquid yielded a "snow" of solid.

Carbon dioxide in combination with nitrogen was known from earlier times as Blackdamp, stythe or choke damp. Along with the other types of damp it was encountered in mining operations and well sinking. Slow oxidation of coal and biological processes replaced the oxygen to create a suffocating mixture of nitrogen and carbon dioxide.

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title: Carbon dioxide