Chalcogens

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 () principally meaning copper (the term was also used for bronze/brass, any metal in the poetic sense, ore or coin), and the Latinized Greek word , 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.

Lighter chalcogens are typically nontoxic in their elemental form, and are often critical to life, while the heavier chalcogens are typically toxic. 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.

Properties

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.

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 their isotopes do not undergo proton emission and some of the most neutron-deficient isotopes of tellurium undergo alpha decay. Polonium's isotopes tend to decay with alpha or beta decay. Isotopes with nuclear spins are more common 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 , 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 (), peroxide ions (), and hydroxide ions (). Sulfur ions generally come in the form of sulfides (), sulfites (), sulfates (), and thiosulfates (). Selenium ions usually come in the form of selenides () and selenates (). Tellurium ions often come in the form of tellurates (). 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 .

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.

Compounds

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 . 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 and , 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 diiodies. 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. 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 photophysic 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 Ti Tl₅Se₈. 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 P_xTe_y 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 n_xE_4xsup>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 .

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