Technetium
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Technetium is a
chemical element A chemical element is a species of atoms that have a given number of protons in their nuclei, including the pure substance consisting only of that species. Unlike chemical compounds, chemical elements cannot be broken down into simpler sub ...
with the symbol Tc and
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
43. It is the lightest element whose isotopes are all
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
. All available technetium is produced as a
synthetic element A synthetic element is one of 24 known chemical elements that do not occur naturally on Earth: they have been created by human manipulation of fundamental particles in a nuclear reactor, a particle accelerator, or the explosion of an atomic bomb; ...
. Naturally occurring technetium is a spontaneous fission product in
uranium ore Uranium ore deposits are economically recoverable concentrations of uranium within the Earth's crust. Uranium is one of the more common elements in the Earth's crust, being 40 times more common than silver and 500 times more common than gold. It ...
and
thorium Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high ...
ore, the most common source, or the product of
neutron capture Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons, ...
in molybdenum ores. This silvery gray, crystalline
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that ca ...
lies between
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
and
rhenium Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
in
group 7 Group 7 may refer to: * G7, an international group of finance minister *Group 7 element, chemical element classification *Halogens (alternative name) *Group 7 Rugby League, rugby league competition in New South Wales, Australia *Group 7 (racing) G ...
of the periodic table, and its chemical properties are intermediate between those of both adjacent elements. The most common naturally occurring isotope is 99Tc, in traces only. Many of technetium's properties had been predicted by Dmitri Mendeleev before it was discovered. Mendeleev noted a gap in his periodic table and gave the undiscovered element the provisional name '' ekamanganese'' (''Em''). In 1937, technetium (specifically the
technetium-97 Technetium (43Tc) is one of the two elements with that have no stable isotopes; the other such element is promethium. – Elements marked with a * have no stable isotope: 43, 61, and 83 and up. It is primarily artificial, with only trace q ...
isotope) became the first predominantly artificial element to be produced, hence its name (from the Greek , '' technetos'', from ''techne'', as in "craft", "art" and having the meaning of "artificial", + One short-lived
gamma ray A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
-emitting
nuclear isomer A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited states have ...
,
technetium-99m Technetium-99m (99mTc) is a metastable nuclear isomer of technetium-99 (itself an isotope of technetium), symbolized as 99mTc, that is used in tens of millions of medical diagnostic procedures annually, making it the most commonly used medical ra ...
, is used in
nuclear medicine Nuclear medicine or nucleology is a medical specialty involving the application of radioactive substances in the diagnosis and treatment of disease. Nuclear imaging, in a sense, is " radiology done inside out" because it records radiation emi ...
for a wide variety of tests, such as bone cancer diagnoses. The ground state of the nuclide
technetium-99 Technetium-99 (99Tc) is an isotope of technetium which decays with a half-life of 211,000 years to stable ruthenium-99, emitting beta particles, but no gamma rays. It is the most significant long-lived fission product of uranium fission, produci ...
is used as a gamma-ray-free source of beta particles. Long-lived technetium isotopes produced commercially are byproducts of the fission of
uranium-235 Uranium-235 (235U or U-235) is an isotope of uranium making up about 0.72% of natural uranium. Unlike the predominant isotope uranium-238, it is fissile, i.e., it can sustain a nuclear chain reaction. It is the only fissile isotope that exi ...
in nuclear reactors and are extracted from nuclear fuel rods. Because even the longest-lived isotope of technetium has a relatively short
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable at ...
(4.21 million years), the 1952 detection of technetium in red giants helped to prove that stars can produce heavier elements.


History


Search for element 43

From the 1860s through 1871, early forms of the periodic table proposed by Dmitri Mendeleev contained a gap between molybdenum (element 42) and
ruthenium Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemical ...
(element 44). In 1871, Mendeleev predicted this missing element would occupy the empty place below
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
and have similar chemical properties. Mendeleev gave it the provisional name ''ekamanganese'' (from ''eka''-, the
Sanskrit Sanskrit (; attributively , ; nominally , , ) is a classical language belonging to the Indo-Aryan branch of the Indo-European languages. It arose in South Asia after its predecessor languages had diffused there from the northwest in the late ...
word for ''one'') because the predicted element was one place down from the known element manganese.


Early misidentifications

Many early researchers, both before and after the periodic table was published, were eager to be the first to discover and name the missing element. Its location in the table suggested that it should be easier to find than other undiscovered elements.


Irreproducible results

German chemists
Walter Noddack Walter Noddack (17 August 1893 – 7 December 1960) was a German chemist. He, Ida Tacke (who later married Noddack), and Otto Berg reported the discovery of element 43 and element 75 in 1925. Rhenium They named element 75 rhenium (Latin ''Rh ...
, Otto Berg, and Ida Tacke reported the discovery of element 75 and element 43 in 1925, and named element 43 ''masurium'' (after
Masuria Masuria (, german: Masuren, Masurian: ''Mazurÿ'') is a ethnographic and geographic region in northern and northeastern Poland, known for its 2,000 lakes. Masuria occupies much of the Masurian Lake District. Administratively, it is part of the ...
in eastern
Prussia Prussia, , Old Prussian: ''Prūsa'' or ''Prūsija'' was a German state on the southeast coast of the Baltic Sea. It formed the German Empire under Prussian rule when it united the German states in 1871. It was ''de facto'' dissolved by an em ...
, now in
Poland Poland, officially the Republic of Poland, is a country in Central Europe. It is divided into 16 administrative provinces called voivodeships, covering an area of . Poland has a population of over 38 million and is the fifth-most populous ...
, the region where Walter Noddack's family originated). The group bombarded
columbite Columbite, also called niobite, niobite-tantalite and columbate [], is a black mineral group that is an ore of niobium. It has a submetallic Lustre (mineralogy), luster and a high density and is a niobate of iron and manganese. This mineral group ...
with a beam of
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no ...
s and deduced element 43 was present by examining
X-ray An X-ray, or, much less commonly, X-radiation, is a penetrating form of high-energy electromagnetic radiation. Most X-rays have a wavelength ranging from 10  picometers to 10  nanometers, corresponding to frequencies in the range 30&nb ...
emission
spectrogram A spectrogram is a visual representation of the spectrum of frequencies of a signal as it varies with time. When applied to an audio signal, spectrograms are sometimes called sonographs, voiceprints, or voicegrams. When the data are represen ...
s. The
wavelength In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats. It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, tro ...
of the X-rays produced is related to the atomic number by a formula derived by
Henry Moseley Henry Gwyn Jeffreys Moseley (; 23 November 1887 – 10 August 1915) was an English physicist, whose contribution to the science of physics was the justification from physical laws of the previous empirical and chemical concept of the atomic num ...
in 1913. The team claimed to detect a faint X-ray signal at a wavelength produced by element 43. Later experimenters could not replicate the discovery, and it was dismissed as an error for many years. Still, in 1933, a series of articles on the discovery of elements quoted the name ''masurium'' for element 43. Whether the 1925 team actually discovered element 43 is still debated.


Official discovery and later history

The
discovery Discovery may refer to: * Discovery (observation), observing or finding something unknown * Discovery (fiction), a character's learning something unknown * Discovery (law), a process in courts of law relating to evidence Discovery, The Discover ...
of element 43 was finally confirmed in a 1937 experiment at the
University of Palermo The University of Palermo ( it, Università degli Studi di Palermo) is a university located in Palermo, Italy, and founded in 1806. It is organized in 12 Faculties. History The University of Palermo was officially founded in 1806, although its ...
in Sicily by Carlo Perrier and
Emilio Segrè Emilio Gino Segrè (1 February 1905 – 22 April 1989) was an Italian-American physicist and Nobel laureate, who discovered the elements technetium and astatine, and the antiproton, a subatomic antiparticle, for which he was awarded the Nobe ...
. In mid-1936, Segrè visited the United States, first
Columbia University Columbia University (also known as Columbia, and officially as Columbia University in the City of New York) is a private research university in New York City. Established in 1754 as King's College on the grounds of Trinity Church in Manhatt ...
in New York and then the Lawrence Berkeley National Laboratory in California. He persuaded
cyclotron A cyclotron is a type of particle accelerator invented by Ernest O. Lawrence in 1929–1930 at the University of California, Berkeley, and patented in 1932. Lawrence, Ernest O. ''Method and apparatus for the acceleration of ions'', filed: Jan ...
inventor
Ernest Lawrence Ernest Orlando Lawrence (August 8, 1901 – August 27, 1958) was an American nuclear physicist and winner of the Nobel Prize in Physics in 1939 for his invention of the cyclotron. He is known for his work on uranium-isotope separation fo ...
to let him take back some discarded cyclotron parts that had become
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
. Lawrence mailed him a molybdenum foil that had been part of the deflector in the cyclotron. Segrè enlisted his colleague Perrier to attempt to prove, through comparative chemistry, that the molybdenum activity was indeed from an element with the atomic number 43. In 1937, they succeeded in isolating the
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numb ...
s technetium-95m and
technetium-97 Technetium (43Tc) is one of the two elements with that have no stable isotopes; the other such element is promethium. – Elements marked with a * have no stable isotope: 43, 61, and 83 and up. It is primarily artificial, with only trace q ...
. University of Palermo officials wanted them to name their discovery "''panormium''", after the
Latin Latin (, or , ) is a classical language belonging to the Italic branch of the Indo-European languages. Latin was originally a dialect spoken in the lower Tiber area (then known as Latium) around present-day Rome, but through the power of the ...
name for
Palermo Palermo ( , ; scn, Palermu , locally also or ) is a city in southern Italy, the capital (political), capital of both the autonomous area, autonomous region of Sicily and the Metropolitan City of Palermo, the city's surrounding metropolitan ...
, ''Panormus''. In 1947 element 43 was named after the
Greek Greek may refer to: Greece Anything of, from, or related to Greece, a country in Southern Europe: *Greeks, an ethnic group. *Greek language, a branch of the Indo-European language family. **Proto-Greek language, the assumed last common ancestor ...
word ''τεχνητός'', meaning "artificial", since it was the first element to be artificially produced. Segrè returned to Berkeley and met
Glenn T. Seaborg Glenn Theodore Seaborg (; April 19, 1912February 25, 1999) was an American chemist whose involvement in the synthesis, discovery and investigation of ten transuranium elements earned him a share of the 1951 Nobel Prize in Chemistry. His work i ...
. They isolated the
metastable isotope A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited states have ha ...
technetium-99m Technetium-99m (99mTc) is a metastable nuclear isomer of technetium-99 (itself an isotope of technetium), symbolized as 99mTc, that is used in tens of millions of medical diagnostic procedures annually, making it the most commonly used medical ra ...
, which is now used in some ten million medical diagnostic procedures annually. In 1952, the astronomer Paul W. Merrill in California detected the
spectral signature Spectral signature is the variation of reflectance or emittance of a material with respect to wavelengths (i.e., reflectance/emittance as a function of wavelength). The spectral signature of stars indicates the composition of the stellar atmosph ...
of technetium (specifically
wavelength In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats. It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, tro ...
s of 403.1  nm, 423.8 nm, 426.2 nm, and 429.7 nm) in light from S-type red giants. The stars were near the end of their lives but were rich in the short-lived element, which indicated that it was being produced in the stars by
nuclear reaction In nuclear physics and nuclear chemistry, a nuclear reaction is a process in which two nuclei, or a nucleus and an external subatomic particle, collide to produce one or more new nuclides. Thus, a nuclear reaction must cause a transformatio ...
s. That evidence bolstered the hypothesis that heavier elements are the product of
nucleosynthesis Nucleosynthesis is the process that creates new atomic nuclei from pre-existing nucleons (protons and neutrons) and nuclei. According to current theories, the first nuclei were formed a few minutes after the Big Bang, through nuclear reactions in ...
in stars. More recently, such observations provided evidence that elements are formed by
neutron capture Neutron capture is a nuclear reaction in which an atomic nucleus and one or more neutrons collide and merge to form a heavier nucleus. Since neutrons have no electric charge, they can enter a nucleus more easily than positively charged protons, ...
in the s-process. Since that discovery, there have been many searches in terrestrial materials for natural sources of technetium. In 1962, technetium-99 was isolated and identified in
pitchblende Uraninite, formerly pitchblende, is a radioactive, uranium-rich mineral and ore with a chemical composition that is largely UO2 but because of oxidation typically contains variable proportions of U3O8. Radioactive decay of the uranium causes t ...
from the
Belgian Congo The Belgian Congo (french: Congo belge, ; nl, Belgisch-Congo) was a Belgian colony in Central Africa from 1908 until independence in 1960. The former colony adopted its present name, the Democratic Republic of the Congo (DRC), in 1964. Colo ...
in extremely small quantities (about 0.2 ng/kg), where it originates as a spontaneous fission product of uranium-238. The
Oklo Oklo is a region near the town of Franceville, in the Haut-Ogooué province of the Central African country of Gabon. Several natural nuclear fission reactors were discovered in the uranium mines in the region in 1972. History Gabon was a Fren ...
natural nuclear fission reactor A natural nuclear fission reactor is a uranium deposit where self-sustaining nuclear chain reactions occur. The conditions under which a natural nuclear reactor could exist had been predicted in 1956 by Japanese American chemist Paul Kuroda. ...
contains evidence that significant amounts of technetium-99 were produced and have since decayed into ruthenium-99.


Characteristics


Physical properties

Technetium is a silvery-gray radioactive
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
with an appearance similar to
platinum Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Pla ...
, commonly obtained as a gray powder. The
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystal, crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pat ...
of the bulk pure metal is
hexagonal In geometry, a hexagon (from Greek , , meaning "six", and , , meaning "corner, angle") is a six-sided polygon. The total of the internal angles of any simple (non-self-intersecting) hexagon is 720°. Regular hexagon A '' regular hexagon'' has ...
close-packed In geometry, close-packing of equal spheres is a dense arrangement of congruent spheres in an infinite, regular arrangement (or lattice). Carl Friedrich Gauss proved that the highest average density – that is, the greatest fraction of space occu ...
. The
crystal structure In crystallography, crystal structure is a description of the ordered arrangement of atoms, ions or molecules in a crystal, crystalline material. Ordered structures occur from the intrinsic nature of the constituent particles to form symmetric pat ...
of the nanodisperse pure metal is cubic. Nanodisperse technetium does not have a split NMR spectrum, while hexagonal bulk technetium has the Tc-99-NMR spectrum split in 9 satellites. Atomic technetium has characteristic
emission lines A spectral line is a dark or bright line in an otherwise uniform and continuous spectrum, resulting from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to iden ...
at
wavelength In physics, the wavelength is the spatial period of a periodic wave—the distance over which the wave's shape repeats. It is the distance between consecutive corresponding points of the same phase on the wave, such as two adjacent crests, tro ...
s of 363.3  nm, 403.1 nm, 426.2 nm, 429.7 nm, and 485.3 nm. The metal form is slightly
paramagnetic Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
, meaning its
magnetic dipoles In electromagnetism, a magnetic dipole is the limit of either a closed loop of electric current or a pair of poles as the size of the source is reduced to zero while keeping the magnetic moment constant. It is a magnetic analogue of the electric ...
align with external magnetic fields, but will assume random orientations once the field is removed. Pure, metallic, single-crystal technetium becomes a
type-II superconductor In superconductivity, a type-II superconductor is a superconductor that exhibits an intermediate phase of mixed ordinary and superconducting properties at intermediate temperature and fields above the superconducting phases. It also features the ...
at temperatures below 7.46  K. Below this temperature, technetium has a very high magnetic penetration depth, greater than any other element except
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
.


Chemical properties

Technetium is located in the seventh group of the periodic table, between
rhenium Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
and
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
. As predicted by the
periodic law Periodic trends are specific patterns that are present in the periodic table that illustrate different aspects of a certain element. They were discovered by the Russian chemist Dmitri Mendeleev in the year 1863. Major periodic trends include atom ...
, its chemical properties are between those two elements. Of the two, technetium more closely resembles rhenium, particularly in its chemical inertness and tendency to form covalent bonds. This is consistent with the tendency of
period 5 element The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with si ...
s to resemble their counterparts in period 6 more than period 4 due to the
lanthanide contraction The lanthanide contraction is the greater-than-expected decrease in atomic radii/ionic radii of the elements in the lanthanide series from atomic number 57, lanthanum, to 71, lutetium, which results in smaller than otherwise expected atomic radii ...
. Unlike manganese, technetium does not readily form cations (
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
s with a net positive charge). Technetium exhibits nine
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s from −1 to +7, with +4, +5, and +7 being the most common. Technetium dissolves in aqua regia,
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
, and concentrated
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
, but it is not soluble in
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
of any concentration. Metallic technetium slowly
tarnish Tarnish is a thin layer of corrosion that forms over copper, brass, aluminum, magnesium, neodymium and other similar metals as their outermost layer undergoes a chemical reaction. Tarnish does not always result from the sole effects of oxygen in ...
es in moist air and, in powder form, burns in
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
. Technetium can catalyse the destruction of hydrazine by
nitric acid Nitric acid is the inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast due to decomposition into oxides of nitrogen. Most commercially available nitri ...
, and this property is due to its multiplicity of valencies. This caused a problem in the separation of plutonium from uranium in nuclear fuel processing, where hydrazine is used as a protective reductant to keep plutonium in the trivalent rather than the more stable tetravalent state. The problem was exacerbated by the mutually enhanced solvent extraction of technetium and zirconium at the previous stage, and required a process modification.


Compounds


Pertechnetate and derivatives

The most prevalent form of technetium that is easily accessible is
sodium pertechnetate Sodium pertechnetate is the inorganic compound with the formula NaTcO4. This colourless salt contains the pertechnetate anion, . The radioactive anion is an important radiopharmaceutical for diagnostic use. The advantages to include its short ha ...
, Na cO4 The majority of this material is produced by radioactive decay from sup>99MoO4sup>2−: : sup>99MoO4sup>2− → sup>99mTcO4sup>− + e
Pertechnetate The pertechnetate ion () is an oxyanion with the chemical formula . It is often used as a convenient water-soluble source of isotopes of the radioactive element technetium (Tc). In particular it is used to carry the 99mTc isotope (half-life 6 hou ...
(tetroxidotechnetate) behaves analogously to perchlorate, both of which are
tetrahedral In geometry, a tetrahedron (plural: tetrahedra or tetrahedrons), also known as a triangular pyramid, is a polyhedron composed of four triangular faces, six straight edges, and four vertex corners. The tetrahedron is the simplest of all the ...
. Unlike
permanganate A permanganate () is a chemical compound containing the manganate(VII) ion, , the conjugate base of permanganic acid. Because the manganese atom is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion is a tr ...
(), it is only a weak
oxidizing agent An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
. Related to pertechnetate is technetium heptoxide. This pale-yellow, volatile solid is produced by oxidation of Tc metal and related precursors: :4 Tc + 7 O2 → 2 Tc2O7 It is a molecular metal oxide, analogous to manganese heptoxide. It adopts a
centrosymmetric In crystallography, a centrosymmetric point group contains an inversion center as one of its symmetry elements. In such a point group, for every point (x, y, z) in the unit cell there is an indistinguishable point (-x, -y, -z). Such point g ...
structure with two types of Tc−O bonds with 167 and 184 pm bond lengths. Technetium heptoxide hydrolyzes to pertechnetate and
pertechnetic acid Pertechnetic acid (HTcO4) is a compound of technetium that is produced by reacting technetium(VII) oxide (Tc2O7) with water or strong oxidizing acids, such as nitric acid, concentrated sulfuric acid or aqua regia. The dark red hygroscopic sub ...
, depending on the pH: :Tc2O7 + 2 OH → 2 TcO4 + H2O :Tc2O7 + H2O → 2 HTcO4 HTcO4 is a strong acid. In concentrated
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
, cO4sup>− converts to the octahedral form TcO3(OH)(H2O)2, the conjugate base of the hypothetical tri
aquo complex In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorat ...
cO3(H2O)3sup>+.


Other chalcogenide derivatives

Technetium forms a dioxide,
disulfide In biochemistry, a disulfide (or disulphide in British English) refers to a functional group with the structure . The linkage is also called an SS-bond or sometimes a disulfide bridge and is usually derived by the coupling of two thiol groups. In ...
, di
selenide A selenide is a chemical compound containing a selenium anion with oxidation number of −2 (Se2−), much as sulfur does in a sulfide. The chemistry of the selenides and sulfides is similar. Similar to sulfide, in aqueous solution, the selenide ion ...
, and di telluride. An ill-defined Tc2S7 forms upon treating
pertechnate The pertechnetate ion () is an oxyanion with the chemical formula . It is often used as a convenient water-soluble source of isotopes of the radioactive element technetium (Tc). In particular it is used to carry the 99mTc isotope (half-life 6 hou ...
with hydrogen sulfide. It thermally decomposes into disulfide and elemental sulfur. Similarly the dioxide can be produced by reduction of the Tc2O7. Unlike the case for rhenium, a trioxide has not been isolated for technetium. However, TcO3 has been identified in the gas phase using mass spectrometry.


Simple hydride and halide complexes

Technetium forms the simple complex . The potassium salt is
isostructural Isostructural chemical compounds have similar chemical structures. " Isomorphous" when used in the relation to crystal structures is not synonymous: in addition to the same atomic connectivity that characterises isostructural compounds, isomorphous ...
with . The following binary (containing only two elements) technetium halides are known: TcF6, TcF5, TcCl4, TcBr4, TcBr3, α-TcCl3, β-TcCl3, TcI3, α-TcCl2, and β-TcCl2. The
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s range from Tc(VI) to Tc(II). Technetium halides exhibit different structure types, such as molecular octahedral complexes, extended chains, layered sheets, and metal clusters arranged in a three-dimensional network. These compounds are produced by combining the metal and halogen or by less direct reactions. TcCl4 is obtained by chlorination of Tc metal or Tc2O7 Upon heating, TcCl4 gives the corresponding Tc(III) and Tc(II) chlorides. :TcCl4 → α-TcCl3 + 1/2 Cl2 :TcCl3 → β-TcCl2 + 1/2 Cl2 The structure of TcCl4 is composed of infinite zigzag chains of edge-sharing TcCl6 octahedra. It is isomorphous to transition metal tetrachlorides of
zirconium Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'' ...
,
hafnium Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri M ...
, and
platinum Platinum is a chemical element with the symbol Pt and atomic number 78. It is a dense, malleable, ductile, highly unreactive, precious, silverish-white transition metal. Its name originates from Spanish , a diminutive of "silver". Pla ...
. Two polymorphs of technetium trichloride exist, α- and β-TcCl3. The α polymorph is also denoted as Tc3Cl9. It adopts a confacial bioctahedral structure. It is prepared by treating the chloro-acetate Tc2(O2CCH3)4Cl2 with HCl. Like Re3Cl9, the structure of the α-polymorph consists of triangles with short M-M distances. β-TcCl3 features octahedral Tc centers, which are organized in pairs, as seen also for
molybdenum trichloride Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals. Synthesis and structure Molybdenum(III) chloride is synthesized by the reduction of molybdenum(V) chloride with hydrogen. A higher yield is pro ...
. TcBr3 does not adopt the structure of either trichloride phase. Instead it has the structure of molybdenum tribromide, consisting of chains of confacial octahedra with alternating short and long Tc—Tc contacts. TcI3 has the same structure as the high temperature phase of TiI3, featuring chains of confacial octahedra with equal Tc—Tc contacts. Several anionic technetium halides are known. The binary tetrahalides can be converted to the hexahalides cX6sup>2− (X = F, Cl, Br, I), which adopt octahedral molecular geometry. More reduced halides form anionic clusters with Tc–Tc bonds. The situation is similar for the related elements of Mo, W, Re. These clusters have the nuclearity Tc4, Tc6, Tc8, and Tc13. The more stable Tc6 and Tc8 clusters have prism shapes where vertical pairs of Tc atoms are connected by triple bonds and the planar atoms by single bonds. Every technetium atom makes six bonds, and the remaining valence electrons can be saturated by one axial and two
bridging ligand In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually ...
halogen atoms such as
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
or
bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table ( halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simi ...
.


Coordination and organometallic complexes

Technetium forms a variety of
coordination complex A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as '' ligands'' or complexing agents. ...
es with organic ligands. Many have been well-investigated because of their relevance to
nuclear medicine Nuclear medicine or nucleology is a medical specialty involving the application of radioactive substances in the diagnosis and treatment of disease. Nuclear imaging, in a sense, is " radiology done inside out" because it records radiation emi ...
. Technetium forms a variety of compounds with Tc–C bonds, i.e. organotechnetium complexes. Prominent members of this class are complexes with CO, arene, and cyclopentadienyl ligands. The binary carbonyl Tc2(CO)10 is a white volatile solid. In this molecule, two technetium atoms are bound to each other; each atom is surrounded by
octahedra In geometry, an octahedron (plural: octahedra, octahedrons) is a polyhedron with eight faces. The term is most commonly used to refer to the regular octahedron, a Platonic solid composed of eight equilateral triangles, four of which meet a ...
of five carbonyl ligands. The bond length between technetium atoms, 303 pm, is significantly larger than the distance between two atoms in metallic technetium (272 pm). Similar
carbonyl In organic chemistry, a carbonyl group is a functional group composed of a carbon atom double-bonded to an oxygen atom: C=O. It is common to several classes of organic compounds, as part of many larger functional groups. A compound containi ...
s are formed by technetium's congeners, manganese and rhenium. Interest in organotechnetium compounds has also been motivated by applications in
nuclear medicine Nuclear medicine or nucleology is a medical specialty involving the application of radioactive substances in the diagnosis and treatment of disease. Nuclear imaging, in a sense, is " radiology done inside out" because it records radiation emi ...
. Technetium also forms aquo-carbonyl complexes, one prominent complex being c(CO)3(H2O)3sup>+, which are unusual compared to other metal carbonyls.


Isotopes

Technetium, with
atomic number The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
''Z'' = 43, is the lowest-numbered element in the periodic table for which all isotopes are
radioactive Radioactive decay (also known as nuclear decay, radioactivity, radioactive disintegration, or nuclear disintegration) is the process by which an unstable atomic nucleus loses energy by radiation. A material containing unstable nuclei is consi ...
. The second-lightest exclusively radioactive element, promethium, has atomic number 61.
Atomic nuclei The atomic nucleus is the small, dense region consisting of protons and neutrons at the center of an atom, discovered in 1911 by Ernest Rutherford based on the 1909 Geiger–Marsden gold foil experiment. After the discovery of the neutron ...
with an odd number of protons are less stable than those with even numbers, even when the total number of
nucleon In physics and chemistry, a nucleon is either a proton or a neutron, considered in its role as a component of an atomic nucleus. The number of nucleons in a nucleus defines the atom's mass number (nucleon number). Until the 1960s, nucleons were ...
s (protons +
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
s) is even, and odd numbered elements have fewer stable
isotope Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numb ...
s. The most stable
radioactive isotopes A radionuclide (radioactive nuclide, radioisotope or radioactive isotope) is a nuclide that has excess nuclear energy, making it unstable. This excess energy can be used in one of three ways: emitted from the nucleus as gamma radiation; transferr ...
are technetium-97 with a
half-life Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable at ...
of 4.21 million years, technetium-98 with 4.2 million years, and technetium-99 with 211,100 years. Thirty other radioisotopes have been characterized with
mass number The mass number (symbol ''A'', from the German word ''Atomgewicht'' tomic weight, also called atomic mass number or nucleon number, is the total number of protons and neutrons (together known as nucleons) in an atomic nucleus. It is approxima ...
s ranging from 85 to 118. Most of these have half-lives that are less than an hour, the exceptions being technetium-93 (2.73 hours), technetium-94 (4.88 hours), technetium-95 (20 hours), and technetium-96 (4.3 days). The primary decay mode for isotopes lighter than technetium-98 (98Tc) is
electron capture Electron capture (K-electron capture, also K-capture, or L-electron capture, L-capture) is a process in which the proton-rich nucleus of an electrically neutral atom absorbs an inner atomic electron, usually from the K or L electron shells. Thi ...
, producing molybdenum (''Z'' = 42). For technetium-98 and heavier isotopes, the primary mode is
beta emission In nuclear physics, beta decay (β-decay) is a type of radioactive decay in which a beta particle (fast energetic electron or positron) is emitted from an atomic nucleus, transforming the original nuclide to an isobar of that nuclide. For exam ...
(the emission of an
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no ...
or positron), producing
ruthenium Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemical ...
(''Z'' = 44), with the exception that technetium-100 can decay both by beta emission and electron capture. Technetium also has numerous
nuclear isomer A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited states have ...
s, which are isotopes with one or more excited nucleons. Technetium-97m (97mTc; "m" stands for
metastability In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball i ...
) is the most stable, with a half-life of 91 days and excitation energy 0.0965 MeV. This is followed by technetium-95m (61 days, 0.03 MeV), and technetium-99m (6.01 hours, 0.142 MeV). Technetium-99m emits only
gamma ray A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
s and decays to technetium-99. Technetium-99 (99Tc) is a major product of the fission of uranium-235 (235U), making it the most common and most readily available isotope of technetium. One gram of technetium-99 produces 6.2×108 disintegrations per second (in other words, the
specific activity Specific activity is the activity per unit mass of a radionuclide and is a physical property of that radionuclide. Activity is a quantity (for which the SI unit is the becquerel) related to radioactivity, and is defined as the number of radi ...
of 99Tc is 0.62 G Bq/g).


Occurrence and production

Technetium occurs naturally in the Earth's crust in minute concentrations of about 0.003 parts per trillion. Technetium is so rare because the
half-lives Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable at ...
of 97Tc and 98Tc are only 4.2 million years. More than a thousand of such periods have passed since the formation of the
Earth Earth is the third planet from the Sun and the only astronomical object known to harbor life. While large volumes of water can be found throughout the Solar System, only Earth sustains liquid surface water. About 71% of Earth's surfa ...
, so the probability of survival of even one atom of primordial technetium is effectively zero. However, small amounts exist as spontaneous fission products in
uranium ore Uranium ore deposits are economically recoverable concentrations of uranium within the Earth's crust. Uranium is one of the more common elements in the Earth's crust, being 40 times more common than silver and 500 times more common than gold. It ...
s. A kilogram of uranium contains an estimated 1 
nanogram To help compare different orders of magnitude, the following lists describe various mass levels between 10−59  kg and 1052 kg. The least massive thing listed here is a graviton, and the most massive thing is the observable universe ...
(10−9 g) equivalent to ten trillion atoms of technetium. Some red giant stars with the spectral types S-, M-, and N contain a spectral absorption line indicating the presence of technetium. These red giants are known informally as
technetium star A technetium star, or more properly a Tc-rich star, is a star whose stellar spectrum contains absorption lines of the light radioactive metal technetium. The most stable isotope of technetium is 97Tc with a half-life of 4.21 million years, which ...
s.


Fission waste product

In contrast to the rare natural occurrence, bulk quantities of technetium-99 are produced each year from spent nuclear fuel rods, which contain various fission products. The fission of a gram of
uranium-235 Uranium-235 (235U or U-235) is an isotope of uranium making up about 0.72% of natural uranium. Unlike the predominant isotope uranium-238, it is fissile, i.e., it can sustain a nuclear chain reaction. It is the only fissile isotope that exi ...
in
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat fr ...
s yields 27 mg of technetium-99, giving technetium a
fission product yield Nuclear fission splits a heavy nucleus such as uranium or plutonium into two lighter nuclei, which are called fission products. Yield refers to the fraction of a fission product produced per fission. Yield can be broken down by: # Individual ...
of 6.1%. Other
fissile In nuclear engineering, fissile material is material capable of sustaining a nuclear fission chain reaction. By definition, fissile material can sustain a chain reaction with neutrons of thermal energy. The predominant neutron energy may be t ...
isotopes produce similar yields of technetium, such as 4.9% from
uranium-233 Uranium-233 (233U or U-233) is a fissile isotope of uranium that is bred from thorium-232 as part of the thorium fuel cycle. Uranium-233 was investigated for use in nuclear weapons and as a reactor fuel. It has been used successfully in exp ...
and 6.21% from
plutonium-239 Plutonium-239 (239Pu or Pu-239) is an isotope of plutonium. Plutonium-239 is the primary fissile isotope used for the production of nuclear weapons, although uranium-235 is also used for that purpose. Plutonium-239 is also one of the three mai ...
. An estimated 49,000 T Bq (78  metric tons) of technetium was produced in nuclear reactors between 1983 and 1994, by far the dominant source of terrestrial technetium. Only a fraction of the production is used commercially. Technetium-99 is produced by the nuclear fission of both uranium-235 and plutonium-239. It is therefore present in
radioactive waste Radioactive waste is a type of hazardous waste that contains radioactive material. Radioactive waste is a result of many activities, including nuclear medicine, nuclear research, nuclear power generation, rare-earth mining, and nuclear weapons r ...
and in the
nuclear fallout Nuclear fallout is the residual radioactive material propelled into the upper atmosphere following a nuclear blast, so called because it "falls out" of the sky after the explosion and the shock wave has passed. It commonly refers to the radioac ...
of
fission bomb A nuclear weapon is an explosive device that derives its destructive force from nuclear reactions, either fission (fission bomb) or a combination of fission and fusion reactions (thermonuclear bomb), producing a nuclear explosion. Both bomb ...
explosions. Its decay, measured in
becquerel The becquerel (; symbol: Bq) is the unit of radioactivity in the International System of Units (SI). One becquerel is defined as the activity of a quantity of radioactive material in which one nucleus decays per second. For applications relatin ...
s per amount of spent fuel, is the dominant contributor to nuclear waste radioactivity after about 104 to 106 years after the creation of the nuclear waste. From 1945 to 1994, an estimated 160 T Bq (about 250 kg) of technetium-99 was released into the environment during atmospheric
nuclear test Nuclear weapons tests are experiments carried out to determine nuclear weapons' effectiveness, Nuclear weapon yield, yield, and explosive capability. Testing nuclear weapons offers practical information about how the weapons function, how detona ...
s. The amount of technetium-99 from nuclear reactors released into the environment up to 1986 is on the order of 1000 TBq (about 1600 kg), primarily by
nuclear fuel reprocessing Nuclear reprocessing is the chemical separation of fission products and actinides from spent nuclear fuel. Originally, reprocessing was used solely to extract plutonium for producing nuclear weapons. With commercialization of nuclear power, the ...
; most of this was discharged into the sea. Reprocessing methods have reduced emissions since then, but as of 2005 the primary release of technetium-99 into the environment is by the Sellafield plant, which released an estimated 550 TBq (about 900 kg) from 1995 to 1999 into the
Irish Sea The Irish Sea or , gv, Y Keayn Yernagh, sco, Erse Sie, gd, Muir Èireann , Ulster-Scots: ''Airish Sea'', cy, Môr Iwerddon . is an extensive body of water that separates the islands of Ireland and Great Britain. It is linked to the Ce ...
. From 2000 onwards the amount has been limited by regulation to 90 TBq (about 140 kg) per year. Discharge of technetium into the sea resulted in contamination of some seafood with minuscule quantities of this element. For example,
European lobster ''Homarus gammarus'', known as the European lobster or common lobster, is a species of clawed lobster from the eastern Atlantic Ocean, Mediterranean Sea and parts of the Black Sea. It is closely related to the American lobster, ''H. americ ...
and fish from west
Cumbria Cumbria ( ) is a ceremonial and non-metropolitan county in North West England, bordering Scotland. The county and Cumbria County Council, its local government, came into existence in 1974 after the passage of the Local Government Act 1972. C ...
contain about 1 Bq/kg of technetium.


Fission product for commercial use

The
metastable In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball i ...
isotope technetium-99m is continuously produced as a fission product from the fission of uranium or
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibi ...
in
nuclear reactor A nuclear reactor is a device used to initiate and control a fission nuclear chain reaction or nuclear fusion reactions. Nuclear reactors are used at nuclear power plants for electricity generation and in nuclear marine propulsion. Heat fr ...
s: : ^_U -> ce^_I + ^_Y + 2^_n : ^_Y -> beta^-1.47\,\ce] ^_Zr -> beta^-2.1\,\ce] ^_Nb -> beta^-15.0\,\ce] ^_Mo -> beta^-65.94\,\ce] ^_Tc -> beta^-211,100\,\ce] ^_Ru Because used fuel is allowed to stand for several years before reprocessing, all molybdenum-99 and technetium-99m is decayed by the time that the fission products are separated from the major
actinide The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The info ...
s in conventional nuclear reprocessing. The liquid left after plutonium–uranium extraction (
PUREX PUREX (plutonium uranium reduction extraction) is a chemical method used to purify fuel for nuclear reactors or nuclear weapons. PUREX is the ''de facto'' standard aqueous nuclear reprocessing method for the recovery of uranium and plutonium ...
) contains a high concentration of technetium as but almost all of this is technetium-99, not technetium-99m. The vast majority of the technetium-99m used in medical work is produced by irradiating dedicated
highly enriched uranium Enriched uranium is a type of uranium in which the percent composition of uranium-235 (written 235U) has been increased through the process of isotope separation. Naturally occurring uranium is composed of three major isotopes: uranium-238 (238U ...
targets in a reactor, extracting molybdenum-99 from the targets in reprocessing facilities, and recovering at the diagnostic center the technetium-99m produced upon decay of molybdenum-99. Molybdenum-99 in the form of molybdate is
adsorbed Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a ...
onto acid alumina () in a shielded column chromatograph inside a
technetium-99m generator A technetium-99m generator, or colloquially a technetium cow or moly cow, is a device used to extract the metastable isotope 99mTc of technetium from a decaying sample of molybdenum-99. 99Mo has a half-life of 66 hours and can be easily transp ...
("technetium cow", also occasionally called a "molybdenum cow"). Molybdenum-99 has a half-life of 67 hours, so short-lived technetium-99m (half-life: 6 hours), which results from its decay, is being constantly produced. The soluble
pertechnetate The pertechnetate ion () is an oxyanion with the chemical formula . It is often used as a convenient water-soluble source of isotopes of the radioactive element technetium (Tc). In particular it is used to carry the 99mTc isotope (half-life 6 hou ...
can then be chemically extracted by
elution In analytical and organic chemistry, elution is the process of extracting one material from another by washing with a solvent; as in washing of loaded ion-exchange resins to remove captured ions. In a liquid chromatography experiment, for exam ...
using a
saline solution Saline (also known as saline solution) is a mixture of sodium chloride (salt) and water. It has a number of uses in medicine including cleaning wounds, removal and storage of contact lenses, and help with dry eyes. By injection into a vein i ...
. A drawback of this process is that it requires targets containing uranium-235, which are subject to the security precautions of fissile materials. Almost two-thirds of the world's supply comes from two reactors; the
National Research Universal Reactor The National Research Universal (NRU) reactor was a 135 MW nuclear research reactor built in the Chalk River Laboratories, Ontario, one of Canada’s national science facilities. It was a multipurpose science facility that served three main roles. ...
at
Chalk River Laboratories Chalk River Laboratories (french: Laboratoires de Chalk River; also known as CRL, Chalk River Labs and formerly Chalk River Nuclear Laboratories, CRNL) is a Canadian nuclear research facility in Deep River, about north-west of Ottawa. CRL is ...
in Ontario, Canada, and the
High Flux Reactor A ''High Flux Reactor'' is a type of nuclear research reactor. * High Flux Isotope Reactor (HFIR), in Oak Ridge, Tennessee, United States of America, * High Flux Australian Reactor (HIFAR), Australia's first nuclear reactor, * High-Flux Advanced Ne ...
at Nuclear Research and Consultancy Group in Petten, Netherlands. All major reactors that produce technetium-99m were built in the 1960s and are close to the end of life. The two new Canadian Multipurpose Applied Physics Lattice Experiment reactors planned and built to produce 200% of the demand of technetium-99m relieved all other producers from building their own reactors. With the cancellation of the already tested reactors in 2008, the future supply of technetium-99m became problematic.


Waste disposal

The long half-life of technetium-99 and its potential to form
anionic An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
species creates a major concern for long-term
disposal of radioactive waste Radioactive waste disposal may refer to: *High-level radioactive waste management * Low-level waste disposal *Ocean disposal of radioactive waste **Ocean floor disposal *Deep borehole disposal *Deep geological repository See also * Radioactive wast ...
. Many of the processes designed to remove fission products in reprocessing plants aim at
cationic An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
species such as caesium (e.g.,
caesium-137 Caesium-137 (), cesium-137 (US), or radiocaesium, is a radioactive isotope of caesium that is formed as one of the more common fission products by the nuclear fission of uranium-235 and other fissionable isotopes in nuclear reactors and nucle ...
) and strontium (e.g.,
strontium-90 Strontium-90 () is a radioactive isotope of strontium produced by nuclear fission, with a half-life of 28.8 years. It undergoes β− decay into yttrium-90, with a decay energy of 0.546 MeV. Strontium-90 has applications in medicine and ...
). Hence the pertechnetate escapes through those processes. Current disposal options favor
burial Burial, also known as interment or inhumation, is a method of final disposition whereby a dead body is placed into the ground, sometimes with objects. This is usually accomplished by excavating a pit or trench, placing the deceased and objec ...
in continental, geologically stable rock. The primary danger with such practice is the likelihood that the waste will contact water, which could leach radioactive contamination into the environment. The anionic pertechnetate and
iodide An iodide ion is the ion I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine de ...
tend not to adsorb into the surfaces of minerals, and are likely to be washed away. By comparison
plutonium Plutonium is a radioactive chemical element with the symbol Pu and atomic number 94. It is an actinide metal of silvery-gray appearance that tarnishes when exposed to air, and forms a dull coating when oxidized. The element normally exhibi ...
,
uranium Uranium is a chemical element with the symbol U and atomic number 92. It is a silvery-grey metal in the actinide series of the periodic table. A uranium atom has 92 protons and 92 electrons, of which 6 are valence electrons. Uranium is weak ...
, and caesium tend to bind to soil particles. Technetium could be immobilized by some environments, such as microbial activity in lake bottom sediments, and the
environmental chemistry Environmental chemistry is the scientific study of the chemical and biochemical phenomena that occur in natural places. It should not be confused with green chemistry, which seeks to reduce potential pollution at its source. It can be defined as ...
of technetium is an area of active research. An alternative disposal method, transmutation, has been demonstrated at
CERN The European Organization for Nuclear Research, known as CERN (; ; ), is an intergovernmental organization that operates the largest particle physics laboratory in the world. Established in 1954, it is based in a northwestern suburb of Gene ...
for technetium-99. In this process, the technetium (technetium-99 as a metal target) is bombarded with
neutron The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
s to form the short-lived technetium-100 (half-life = 16 seconds) which decays by beta decay to stable
ruthenium Ruthenium is a chemical element with the symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to most other chemical ...
-100. If recovery of usable ruthenium is a goal, an extremely pure technetium target is needed; if small traces of the
minor actinide The minor actinides are the actinide elements in used nuclear fuel other than uranium and plutonium, which are termed the major actinides. The minor actinides include neptunium (element 93), americium (element 95), curium (element 96), berkeliu ...
s such as americium and curium are present in the target, they are likely to undergo fission and form more fission products which increase the radioactivity of the irradiated target. The formation of ruthenium-106 (half-life 374 days) from the 'fresh fission' is likely to increase the activity of the final ruthenium metal, which will then require a longer cooling time after irradiation before the ruthenium can be used. The actual separation of technetium-99 from spent nuclear fuel is a long process. During fuel reprocessing, it comes out as a component of the highly radioactive waste liquid. After sitting for several years, the radioactivity reduces to a level where extraction of the long-lived isotopes, including technetium-99, becomes feasible. A series of chemical processes yields technetium-99 metal of high purity.


Neutron activation

Molybdenum-99 Molybdenum (42Mo) has 33 known isotopes, ranging in atomic mass from 83 to 115, as well as four metastable nuclear isomers. Seven isotopes occur naturally, with atomic masses of 92, 94, 95, 96, 97, 98, and 100. All unstable isotopes of molybdenum ...
, which decays to form technetium-99m, can be formed by the
neutron activation Neutron activation is the process in which neutron radiation induces radioactivity in materials, and occurs when atomic nuclei capture free neutrons, becoming heavier and entering excited states. The excited nucleus decays immediately by emit ...
of molybdenum-98. When needed, other technetium isotopes are not produced in significant quantities by fission, but are manufactured by neutron irradiation of parent isotopes (for example, technetium-97 can be made by neutron irradiation of ruthenium-96).


Particle accelerators

The feasibility of technetium-99m production with the 22-MeV-proton bombardment of a molybdenum-100 target in medical cyclotrons following the reaction 100Mo(p,2n)99mTc was demonstrated in 1971. The recent shortages of medical technetium-99m reignited the interest in its production by proton bombardment of isotopically enriched (>99.5%) molybdenum-100 targets. Other techniques are being investigated for obtaining molybdenum-99 from molybdenum-100 via (n,2n) or (γ,n) reactions in particle accelerators.


Applications


Nuclear medicine and biology

Technetium-99m Technetium-99m (99mTc) is a metastable nuclear isomer of technetium-99 (itself an isotope of technetium), symbolized as 99mTc, that is used in tens of millions of medical diagnostic procedures annually, making it the most commonly used medical ra ...
("m" indicates that this is a
metastable In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball i ...
nuclear isomer) is used in radioactive isotope medical tests. For example, Technetium-99m is a
radioactive tracer A radioactive tracer, radiotracer, or radioactive label is a chemical compound in which one or more atoms have been replaced by a radionuclide so by virtue of its radioactive decay it can be used to explore the mechanism of chemical reactions by ...
that medical imaging equipment tracks in the human body. It is well suited to the role because it emits readily detectable 140 
keV Kev can refer to: Given name * Kev Adams, French comedian, actor, screenwriter and film producer born Kevin Smadja in 1991 * Kevin Kev Carmody (born 1946), Indigenous Australian singer-songwriter * Kev Coghlan (born 1988), Scottish Grand Prix moto ...
gamma ray A gamma ray, also known as gamma radiation (symbol γ or \gamma), is a penetrating form of electromagnetic radiation arising from the radioactive decay of atomic nuclei. It consists of the shortest wavelength electromagnetic waves, typically ...
s, and its half-life is 6.01 hours (meaning that about 94% of it decays to technetium-99 in 24 hours). The chemistry of technetium allows it to be bound to a variety of biochemical compounds, each of which determines how it is metabolized and deposited in the body, and this single isotope can be used for a multitude of diagnostic tests. More than 50 common
radiopharmaceuticals Radiopharmaceuticals, or medicinal radiocompounds, are a group of pharmaceutical drugs containing radioactive isotopes. Radiopharmaceuticals can be used as diagnostic and therapeutic agents. Radiopharmaceuticals emit radiation themselves, which is ...
are based on technetium-99m for imaging and functional studies of the
brain A brain is an organ that serves as the center of the nervous system in all vertebrate and most invertebrate animals. It is located in the head, usually close to the sensory organs for senses such as vision. It is the most complex organ in a ve ...
, heart muscle,
thyroid The thyroid, or thyroid gland, is an endocrine gland in vertebrates. In humans it is in the neck and consists of two connected lobes. The lower two thirds of the lobes are connected by a thin band of tissue called the thyroid isthmus. The thy ...
,
lungs The lungs are the primary organs of the respiratory system in humans and most other animals, including some snails and a small number of fish. In mammals and most other vertebrates, two lungs are located near the backbone on either side ...
,
liver The liver is a major Organ (anatomy), organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the Protein biosynthesis, synthesis of proteins and biochemicals necessary for ...
,
gall bladder In vertebrates, the gallbladder, also known as the cholecyst, is a small hollow organ where bile is stored and concentrated before it is released into the small intestine. In humans, the pear-shaped gallbladder lies beneath the liver, although ...
,
kidney The kidneys are two reddish-brown bean-shaped organs found in vertebrates. They are located on the left and right in the retroperitoneal space, and in adult humans are about in length. They receive blood from the paired renal arteries; blood ...
s,
skeleton A skeleton is the structural frame that supports the body of an animal. There are several types of skeletons, including the exoskeleton, which is the stable outer shell of an organism, the endoskeleton, which forms the support structure inside ...
,
blood Blood is a body fluid in the circulatory system of humans and other vertebrates that delivers necessary substances such as nutrients and oxygen to the cells, and transports metabolic waste products away from those same cells. Blood in the cir ...
, and
tumor A neoplasm () is a type of abnormal and excessive growth of tissue. The process that occurs to form or produce a neoplasm is called neoplasia. The growth of a neoplasm is uncoordinated with that of the normal surrounding tissue, and persists ...
s. The longer-lived isotope, technetium-95m with a half-life of 61 days, is used as a
radioactive tracer A radioactive tracer, radiotracer, or radioactive label is a chemical compound in which one or more atoms have been replaced by a radionuclide so by virtue of its radioactive decay it can be used to explore the mechanism of chemical reactions by ...
to study the movement of technetium in the environment and in plant and animal systems.


Industrial and chemical

Technetium-99 decays almost entirely by beta decay, emitting beta particles with consistent low energies and no accompanying gamma rays. Moreover, its long half-life means that this emission decreases very slowly with time. It can also be extracted to a high chemical and isotopic purity from radioactive waste. For these reasons, it is a National Institute of Standards and Technology (NIST) standard beta emitter, and is used for equipment calibration. Technetium-99 has also been proposed for optoelectronic devices and nanotechnology, nanoscale nuclear battery, nuclear batteries. Like
rhenium Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
and palladium, technetium can serve as a catalyst. In processes such as the dehydrogenation of isopropyl alcohol, it is a far more effective catalyst than either rhenium or palladium. However, its radioactivity is a major problem in safe catalytic applications. When steel is immersed in water, adding a small concentration (55 parts per notation, ppm) of potassium pertechnetate(VII) to the water protects the steel from corrosion, even if the temperature is raised to . For this reason, pertechnetate has been used as an anodic corrosion inhibitor for steel, although technetium's radioactivity poses problems that limit this application to self-contained systems. While (for example) can also inhibit corrosion, it requires a concentration ten times as high. In one experiment, a specimen of carbon steel was kept in an aqueous solution of pertechnetate for 20 years and was still uncorroded. The mechanism by which pertechnetate prevents corrosion is not well understood, but seems to involve the reversible formation of a thin surface layer (Passivation (chemistry), passivation). One theory holds that the pertechnetate reacts with the steel surface to form a layer of technetium oxide, dioxide which prevents further corrosion; the same effect explains how iron powder can be used to remove pertechnetate from water. The effect disappears rapidly if the concentration of pertechnetate falls below the minimum concentration or if too high a concentration of other ions is added. As noted, the radioactive nature of technetium (3 MBq/L at the concentrations required) makes this corrosion protection impractical in almost all situations. Nevertheless, corrosion protection by pertechnetate ions was proposed (but never adopted) for use in boiling water reactors.


Precautions

Technetium plays no natural biological role and is not normally found in the human body. Technetium is produced in quantity by nuclear fission, and spreads more readily than many radionuclides. It appears to have low chemical toxicity. For example, no significant change in blood formula, body and organ weights, and food consumption could be detected for rats which ingested up to 15 µg of technetium-99 per gram of food for several weeks. In the body, technetium quickly gets converted to the stable ion, which is highly water-soluble and quickly excreted. The radiological toxicity of technetium (per unit of mass) is a function of compound, type of radiation for the isotope in question, and the isotope's half-life. All isotopes of technetium must be handled carefully. The most common isotope, technetium-99, is a weak beta emitter; such radiation is stopped by the walls of laboratory glassware. The primary hazard when working with technetium is inhalation of dust; such radioactive contamination in the lungs can pose a significant cancer risk. For most work, careful handling in a fume hood is sufficient, and a glove box is not needed.


Notes


References


Bibliography

* * * *


Further reading

* * * *
EnvironmentalChemistry.com – Technetium
!--per the guidelines a
Wikipedia's WikiProject Elements
(all viewed 1 December 2002)-->
Nudat 2
nuclide chart from the National Nuclear Data Center, Brookhaven National Laboratory


External links



at ''The Periodic Table of Videos'' (University of Nottingham) {{Authority control Technetium, Chemical elements Transition metals Synthetic elements Radiopharmaceuticals Chemical elements predicted by Dmitri Mendeleev Chemical elements with hexagonal close-packed structure