Technetium (99mTc) Furifosmin
   HOME

TheInfoList



OR:

Technetium is a chemical element; 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 43. It is the lightest element whose isotopes are all radioactive. 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 ore (the most common source), or the product of neutron capture 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 lies between manganese 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-emitting nuclear isomer, technetium-99m, is used in nuclear medicine 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 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 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 (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 and have similar chemical properties. Mendeleev gave it the provisional name ''ekamanganese'' (from ''eka''-, the Sanskrit 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 in eastern Prussia, now in Poland, 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 with a beam of electrons and deduced element 43 was present by examining X-ray emission spectrograms. The wavelength 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 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 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. 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 isotopes
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. University of Palermo officials wanted them to name their discovery "''panormium''", after the Latin 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 technetium-99m, 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 wavelengths 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 reactions. 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 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 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 with an appearance similar to platinum, commonly obtained as a gray powder. The crystal structure of the bulk pure metal is hexagonal
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 at wavelengths 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. 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 ( ions with a net positive charge). Technetium exhibits nine oxidation states from −1 to +7, with +4, +5, and +7 being the most common. Technetium dissolves in aqua regia, nitric acid, 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 of any concentration. Metallic technetium slowly tarnishes in moist air and, in powder form, burns in oxygen. When reacting with hydrogen at high pressure, it forms the hydride TcH1.3 while reacting with carbon 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, 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 (), it is only a weak oxidizing agent. 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 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 states 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, hafnium, and platinum. 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 or bromine.


Coordination and organometallic complexes

Technetium forms a variety of coordination complexes with organic ligands. Many have been well-investigated because of their relevance to nuclear medicine. 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. 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 ''Z'' = 43, is the lowest-numbered element in the periodic table for which all isotopes are radioactive. 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 + neutrons) is even, and odd numbered elements have fewer stable isotopes. The most stable radioactive isotopes are technetium-97 with a half-life 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, 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 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 rays 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, 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 in nuclear reactors yields 27 mg of technetium-99, giving technetium a fission product yield 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 and in the nuclear fallout of fission 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; 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. 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 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 in nuclear reactors: : ^_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 actinides 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 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 ("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. 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 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, uranium, 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 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 neutrons 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 actinides 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, which decays to form technetium-99m, can be formed by the neutron activation 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 ("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 that medical imaging equipment tracks in the human body. It is well suited to the role because it emits readily detectable 140  keV gamma rays, 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 are based on technetium-99m for imaging and functional studies of the brain, heart muscle, thyroid, lungs, liver, gall bladder, kidneys,
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, and tumors. The longer-lived isotope, technetium-95m with a half-life of 61 days, is used as a radioactive tracer 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 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, 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  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 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 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