Technetium (99mTc) Galtifenin
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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 ...
; it has
symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, object, or relationship. Symbols allow people to go beyond what is known or seen by creating linkages between otherwise very different conc ...
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 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 numbers) ...
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 consid ...
. Technetium and
promethium Promethium is a chemical element with the symbol Pm and atomic number 61. All of its isotopes are radioactive; it is extremely rare, with only about 500–600 grams naturally occurring in Earth's crust at any given time. Promethium is one of onl ...
are the only radioactive elements whose neighbours in the sense of atomic number are both stable. All available technetium is produced as a synthetic element. Naturally occurring technetium is a spontaneous
fission product Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
in uranium ore 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 me ...
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 Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...
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 can ...
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 in group 7 of the
periodic table The periodic table, also known as the periodic table of the (chemical) elements, is a rows and columns arrangement of the chemical elements. It is widely used in chemistry, physics, and other sciences, and is generally seen as an icon of ch ...
, 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 Dmitri Ivanovich Mendeleev (sometimes transliterated as Mendeleyev or Mendeleef) ( ; russian: links=no, Дмитрий Иванович Менделеев, tr. , ; 8 February Old_Style_and_New_Style_dates">O.S._27_January.html" ;"title="O ...
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 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,
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 emitting ...
for a wide variety of tests, such as bone cancer diagnoses. The ground state of the
nuclide A nuclide (or nucleide, from nucleus, also known as nuclear species) is a class of atoms characterized by their number of protons, ''Z'', their number of neutrons, ''N'', and their nuclear energy state. The word ''nuclide'' was coined by Truman ...
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, produc ...
is used as a gamma-ray-free source of
beta particle A beta particle, also called beta ray or beta radiation (symbol β), is a high-energy, high-speed electron or positron emitted by the radioactive decay of an atomic nucleus during the process of beta decay. There are two forms of beta decay, β∠...
s. Long-lived technetium isotopes produced commercially are byproducts of the
fission Fission, a splitting of something into two or more parts, may refer to: * Fission (biology), the division of a single entity into two or more parts and the regeneration of those parts into separate entities resembling the original * Nuclear fissio ...
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 exis ...
in
nuclear reactors 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 from nu ...
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 ato ...
(4.21 million years), the 1952 detection of technetium in
red giant A red giant is a luminous giant star of low or intermediate mass (roughly 0.3–8 solar masses ()) in a late phase of stellar evolution. The outer atmosphere is inflated and tenuous, making the radius large and the surface temperature around or ...
s helped to prove that stars can produce heavier elements.


History


Early assumptions

From the 1860s through 1871, early forms of the periodic table proposed by
Dmitri Mendeleev Dmitri Ivanovich Mendeleev (sometimes transliterated as Mendeleyev or Mendeleef) ( ; russian: links=no, Дмитрий Иванович Менделеев, tr. , ; 8 February Old_Style_and_New_Style_dates">O.S._27_January.html" ;"title="O ...
contained a gap between
molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...
(element 42) and ruthenium (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 ''Rhe ...
, Otto Berg, and
Ida Tacke Ida Noddack (25 February 1896 – 24 September 1978), ''née'' Tacke, was a German chemist and physicist. In 1934 she was the first to mention the idea later named nuclear fission. With her husband - Walter Noddack - and Otto Berg (scientist), ...
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). This name caused significant resentment in the scientific community, because it was interpreted as referring to victories of the German army over the Russian army in the Masuria region during World War I; as the Noddacks remained in their academic positions while the Nazis were in power, suspicions and hostility against their claim for discovering element 43 continued. 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 w ...
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 kn ...
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 spectrograms. 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 In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
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. Still, in 1933, a series of articles on the discovery of elements quoted the name ''masurium'' for element 43. Some more recent attempts have been made to rehabilitate the Noddacks' claims, but they are disproved by
Paul Kuroda Paul Kazuo Kuroda (1 April 1917 – 16 April 2001), was a Japanese-American chemist and nuclear scientist. Life He was born on April 1, 1917 in Fukuoka Prefecture, Japan. He died on April 16, 2001 at his home in Las Vegas, Nevada. Career He ...
's study on the amount of technetium that could have been present in the ores they studied: it could not have exceeded 3 × 10−11 μg/kg of ore, and thus would have been undetectable by the Noddacks' methods. Eric Scerri, ''A tale of seven elements,'' (Oxford University Press 2013) , pp. 109–114, 125–131


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 Discovery ...
of element 43 was finally confirmed in a 1937 experiment at the University of Palermo in Sicily by
Carlo Perrier Carlo Perrier (born July 7, 1886 in Turin , † May 22, 1948 in Genoa ) was an Italian mineralogist and chemist who did extensive research on the element technetium. With the discovery of technetium in 1937, he and Emilio Segrè Emilio Gino S ...
and Emilio Segrè. 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 Lawrence Berkeley National Laboratory (LBNL), commonly referred to as the Berkeley Lab, is a United States Department of Energy National Labs, United States national laboratory that is owned by, and conducts scientific research on behalf of, t ...
in California. He persuaded cyclotron inventor
Ernest Lawrence Ernest Orlando Lawrence (August 8, 1901 â€“ 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 f ...
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 consid ...
. Lawrence mailed him a
molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...
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 numbers) ...
s
technetium-95 Technetium (43Tc) is one of the two elements with that have no stable isotopes; the other such element is promethium. â€“ Elements marked with a * have no stable isotope: 43, 61, and 83 and up. It is primarily artificial, with only trace qu ...
m and
technetium-97 Technetium (43Tc) is one of the two elements with that have no stable isotopes; the other such element is promethium. â€“ Elements marked with a * have no stable isotope: 43, 61, and 83 and up. It is primarily artificial, with only trace qu ...
. 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 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 in ...
. 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 excited state, higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited ...
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 Paul Willard Merrill (August 15, 1887 – July 19, 1961) was an American astronomer whose specialty was spectroscopy. He was the first to define S-type stars in 1922. Career He received his Ph.D. at the University of California (now UC Berkeley) ...
in California detected the spectral signature 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 giant A red giant is a luminous giant star of low or intermediate mass (roughly 0.3–8 solar masses ()) in a late phase of stellar evolution. The outer atmosphere is inflated and tenuous, making the radius large and the surface temperature around or ...
s. 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 atomic nucleus, nuclei, or a nucleus and an external subatomic particle, collide to produce one or more new nuclides. Thus, a nuclear reaction must cause a t ...
s. That evidence bolstered the hypothesis that heavier elements are the product of nucleosynthesis 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 The slow neutron-capture process, or ''s''-process, is a series of reactions in nuclear astrophysics that occur in stars, particularly asymptotic giant branch stars. The ''s''-process is responsible for the creation (nucleosynthesis) of approximat ...
. 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 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 very small quantities (about 0.2 ng/kg), where it originates as a
spontaneous fission Spontaneous fission (SF) is a form of radioactive decay that is found only in very heavy chemical elements. The nuclear binding energy of the elements reaches its maximum at an atomic mass number of about 56 (e.g., iron-56); spontaneous breakdo ...
product of
uranium-238 Uranium-238 (238U or U-238) is the most common isotope of uranium found in nature, with a relative abundance of 99%. Unlike uranium-235, it is non-fissile, which means it cannot sustain a chain reaction in a thermal-neutron reactor. However, it ...
. 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 French ...
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. Th ...
contains evidence that significant amounts of technetium-99 were produced and have since decayed into
ruthenium-99 Naturally occurring ruthenium (44Ru) is composed of seven stable isotopes. Additionally, 27 radioactive isotopes have been discovered. Of these radioisotopes, the most stable are 106Ru, with a half-life of 373.59 days; 103Ru, with a half-life of 3 ...
.


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". Platinu ...
, 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 ...
, and crystal structures of the nanodisperse pure metal are
cubic Cubic may refer to: Science and mathematics * Cube (algebra), "cubic" measurement * Cube, a three-dimensional solid object bounded by six square faces, facets or sides, with three meeting at each vertex ** Cubic crystal system, a crystal system w ...
. 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 unit cell parameters of the orthorhombic Tc metal were reported when Tc is contaminated with carbon (a = 0.2805(4), b = 0.4958(8), c = 0.4474(5)·nm for Tc-C with 1.38 wt% C and a = 0.2815(4), b = 0.4963(8), c = 0.4482(5) •nm for Tc-C with 1.96 wt% C ). The metal form is slightly paramagnetic, 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 field A magnetic field is a vector field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular to its own velocity and to ...
s, 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 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, 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 bond A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
s. This is consistent with the tendency of period 5 elements to resemble their counterparts in period 6 more than period 4 due to the lanthanide contraction. Unlike manganese, technetium does not readily form
cation 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 ...
s (
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 conven ...
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 tarnishes 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 ...
. When reacting with
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
at high pressure, it forms the hydride TcH1.3 while reacting with
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
it forms Tc6C, with cell parameter 3.98 Ã…, as well the nanodisperce low-carbon-content carbide with parameter 4.02 Ã…. Technetium can catalyse the destruction of
hydrazine Hydrazine is an inorganic compound with the chemical formula . It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour. Hydrazine is highly toxic unless handled in solution as, for example, 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 () is only weakly hydrated in aqueous solutions, and it behaves analogously to perchlorate anion, both of which are tetrahedral. 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 tra ...
(), 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 "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
. Related to pertechnetate is
technetium heptoxide Technetium(VII) oxide is the chemical compound with the formula Tc2O7. This yellow volatile solid is a rare example of a molecular binary metal oxide, the other examples being RuO4, OsO4, and the unstable Mn2O7. It adopts a centrosymmetric co ...
. 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 Manganese(VII) oxide (manganese heptoxide) is an inorganic compound with the formula Mn2O7. This volatile liquid is highly reactive. It is a dangerous oxidizer and was first described in 1860. It is the acid anhydride of permanganic acid. Prop ...
. 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 groups ...
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 cO3(H2O)3sup>+.


Other chalcogenide derivatives

Technetium forms a
dioxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
, disulfide, di selenide, 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 Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...
.


Simple hydride and halide complexes

Technetium forms the simple complex . The potassium salt is isostructural with . At high pressure formation of TcH1,3 from elements was also reported. 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". Platinu ...
. Two polymorphs of
technetium trichloride Technetium trichloride is an inorganic compound of technetium and chlorine with the formula TcCl3. Preparation and properties Two polymorphs of technetium trichloride are known. The α-polymorph is prepared as a black solid from ditechnetium(I ...
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. TcBr3 does not adopt the structure of either trichloride phase. Instead it has the structure of
molybdenum tribromide Molybdenum(III) bromide is the inorganic compound with the formula MoBr3. It is a black solid that is insoluble in most solvents but dissolves in donor solvents such as pyridine. Preparation Molybdenum(III) bromide is produced by the reaction of ...
, 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 In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The oc ...
. 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 r ...
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 simila ...
.


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. Many ...
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 emitting ...
. 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 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 carbonyls 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 emitting ...
. 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 consid ...
. The second-lightest exclusively radioactive element,
promethium Promethium is a chemical element with the symbol Pm and atomic number 61. All of its isotopes are radioactive; it is extremely rare, with only about 500–600 grams naturally occurring in Earth's crust at any given time. Promethium is one of onl ...
, 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
proton A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s are less stable than those with even numbers, even when the total number of nucleons (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 numbers) ...
s. The most stable radioactive isotopes 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 ato ...
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 numbers 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 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 consid ...
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 Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...
(''Z'' = 42). For technetium-98 and heavier isotopes, the primary mode is beta emission (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 kn ...
or
positron The positron or antielectron is the antiparticle or the antimatter counterpart of the electron. It has an electric charge of +1 '' e'', a spin of 1/2 (the same as the electron), and the same mass as an electron. When a positron collides ...
), producing ruthenium (''Z'' = 44), with the exception that technetium-100 can decay both by beta emission and electron capture. Technetium also has numerous nuclear isomers, which are isotopes with one or more excited nucleons. Technetium-97m (97mTc; "m" stands for metastability) 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 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 Primordial may refer to: * Primordial era, an era after the Big Bang. See Chronology of the universe * Primordial sea (a.k.a. primordial ocean, ooze or soup). See Abiogenesis * Primordial nuclide, nuclides, a few radioactive, that formed before ...
technetium is effectively zero. However, small amounts exist as spontaneous
fission product Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
s in uranium ores. A kilogram of uranium contains an estimated 1  nanogram (10−9 g) equivalent to ten trillion atoms of technetium. Some
red giant A red giant is a luminous giant star of low or intermediate mass (roughly 0.3–8 solar masses ()) in a late phase of stellar evolution. The outer atmosphere is inflated and tenuous, making the radius large and the surface temperature around or ...
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 exis ...
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 from nu ...
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 i ...
of 6.1%. Other fissile isotopes produce similar yields of technetium, such as 4.9% from uranium-233 and 6.21% from plutonium-239. An estimated 49,000 T Bq (78 
metric tons The tonne ( or ; symbol: t) is a unit of mass equal to 1000 kilograms. It is a non-SI unit accepted for use with SI. It is also referred to as a metric ton to distinguish it from the non-metric units of the short ton ( United States ...
) 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 Nuclear fission is a reaction in which the nucleus of an atom splits into two or more smaller nuclei. The fission process often produces gamma photons, and releases a very large amount of energy even by the energetic standards of radio ...
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 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 becquerels 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 tests. 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 Sellafield is a large multi-function nuclear site close to Seascale on the coast of Cumbria, England. As of August 2022, primary activities are nuclear waste processing and storage and nuclear decommissioning. Former activities included nucle ...
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 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. Cumb ...
contain about 1 Bq/kg of technetium.


Fission product for commercial use

The metastable isotope technetium-99m is continuously produced as a
fission product Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
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 from nu ...
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 inform ...
s in conventional
nuclear 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 ...
. 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 fr ...
) 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 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 transpo ...
("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 can then be chemically extracted by elution 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 it ...
. 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 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 a ...
in Ontario, Canada, and the High Flux Reactor at
Nuclear Research and Consultancy Group Nuclear Research and Consultancy Group (NRG) is a Dutch institute that performs nuclear research for the government and private companies. It is the most important producer of radionuclides, such as molybdenum-99, lutetium-177 and iridium-192, in Eu ...
in Petten, Netherlands. All major reactors that produce technetium-99m were built in the 1960s and are close to the
end of life End-of-life may refer to: * End-of-life (product), a term used with respect to terminating the sale or support of goods and services * End-of-life care, medical care for patients with terminal illnesses or conditions that have become advanced, prog ...
. The two new Canadian
Multipurpose Applied Physics Lattice Experiment The Multipurpose Applied Physics Lattice Experiment (MAPLE), later renamed MDS Medical Isotope Reactors (MMIR), was a dedicated isotope-production facility built by AECL and MDS Nordion. It was intended to include two identical reactors, as well ...
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 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 species such as
caesium Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
(e.g., caesium-137) and
strontium Strontium is the chemical element with the symbol Sr and atomic number 38. An alkaline earth metal, strontium is a soft silver-white yellowish metallic element that is highly chemically reactive. The metal forms a dark oxide layer when it is ex ...
(e.g., strontium-90). 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 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 Caesium (IUPAC spelling) (or cesium in American English) is a chemical element with the symbol Cs and atomic number 55. It is a soft, silvery-golden alkali metal with a melting point of , which makes it one of only five elemental metals that a ...
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 t ...
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-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 Americium is a synthetic radioactive chemical element with the symbol Am and atomic number 95. It is a transuranic member of the actinide series, in the periodic table located under the lanthanide element europium, and thus by analogy was na ...
and
curium Curium is a transuranic, radioactive chemical element with the symbol Cm and atomic number 96. This actinide element was named after eminent scientists Marie and Pierre Curie, both known for their research on radioactivity. Curium was first inte ...
are present in the target, they are likely to undergo fission and form more
fission product Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
s 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 emittin ...
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 Naturally occurring ruthenium (44Ru) is composed of seven stable isotopes. Additionally, 27 radioactive isotopes have been discovered. Of these radioisotopes, the most stable are 106Ru, with a half-life of 373.59 days; 103Ru, with a half-life of 3 ...
).


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 nuclear isomer) is used in radioactive isotope
medical tests A medical test is a medical procedure performed to detect, diagnose, or monitor diseases, disease processes, susceptibility, or to determine a course of treatment. Medical tests such as, physical and visual exams, diagnostic imaging, genetic te ...
. 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
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 v ...
, 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 of th ...
,
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,
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 c ...
, 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 The National Institute of Standards and Technology (NIST) is an agency of the United States Department of Commerce whose mission is to promote American innovation and industrial competitiveness. NIST's activities are organized into physical sci ...
(NIST) standard beta emitter, and is used for equipment calibration. Technetium-99 has also been proposed for optoelectronic devices and nanoscale
nuclear batteries Nuclear may refer to: Physics Relating to the Atomic nucleus, nucleus of the atom: *Nuclear engineering *Nuclear physics *Nuclear power *Nuclear reactor *Nuclear weapon *Nuclear medicine *Radiation therapy *Nuclear warfare Mathematics *Nuclear ...
. Like rhenium and
palladium Palladium is a chemical element with the symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1803 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas, which was itself na ...
, technetium can serve as a
catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
. In processes such as the
dehydrogenation In chemistry, dehydrogenation is a chemical reaction that involves the removal of hydrogen, usually from an organic molecule. It is the reverse of hydrogenation. Dehydrogenation is important, both as a useful reaction and a serious problem. At ...
of
isopropyl alcohol Isopropyl alcohol (IUPAC name propan-2-ol and also called isopropanol or 2-propanol) is a colorless, flammable organic compound with a pungent alcoholic odor. As an isopropyl group linked to a hydroxyl group (chemical formula ) it is the simple ...
, 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  ppm) of potassium pertechnetate(VII) to the water protects the
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
from corrosion, even if the temperature is raised to . For this reason, pertechnetate has been used as an anodic
corrosion Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
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). One theory holds that the pertechnetate reacts with the steel surface to form a layer of
technetium dioxide Technetium(IV) oxide, also known as technetium dioxide, is a chemical compound with the formula TcO2 which forms the dihydrate, TcO2·2H2O, which is also known as technetium(IV) hydroxide. It is a radioactive black solid which slowly oxidizes in ...
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 Âµg 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 A fume hood (sometimes called a fume cupboard or fume closet) is a type of local ventilation device that is designed to limit exposure to hazardous or toxic fumes, vapors or dusts. Description A fume hood is typically a large piece of equipmen ...
is sufficient, and a glove box is not needed.


Notes


References


Bibliography

* * * * *


Further reading

* * * *
EnvironmentalChemistry.com â€“ 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 Chemical elements Transition metals Synthetic elements Chemical elements predicted by Dmitri Mendeleev Chemical elements with hexagonal close-packed structure