Many of technetium’s properties were predicted by
Dmitri Mendeleev before the element was discovered. Mendeleev noted a gap in his
periodic table and gave the undiscovered element the provisional name
ekamanganese (Em). In 1937, technetium (specifically the
technetium-97 isotope) became the first predominantly artificial element to be produced, hence its name (from the
Greek τεχνητός, meaning “artificial”).
Search for element 43
From the 1860s through 1871, early forms of the periodic table proposed by Dimitri Mendeleev contained a gap between
molybdenum (element 42) and
ruthenium(element 44). In 1871, Mendeleev predicted this missing element would occupy the empty place below
manganese and therefore have similar chemical properties. Mendeleev gave it the provisional name ekamanganese (fromeka-, the
Sanskrit word for one, because the predicted element was one place down from the known element manganese.)
[3]
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. It was first thought to have been found in
platinum ores in 1828 and was given the name
polinium, but turned out to be impure
iridium. Then, in 1846, the element
ilmenium was claimed to have been discovered, but later was determined to be impure
niobium. This mistake was repeated in 1847 with the “discovery” of
pelopium.
[4]
In 1877, the Russian chemist Serge Kern reported discovering the missing element in platinum ore. Kern named what he thought was the new element
davyum (after the noted English chemist Sir
Humphry Davy), but it was eventually determined to be a mixture of
iridium,
rhodium and
iron. Another candidate,
lucium, followed in 1896, but it was determined to be
yttrium. Then in 1908, the Japanese chemist
Masataka Ogawa found evidence in the mineral
thorianite, which he thought indicated the presence of element 43. Ogawa named the element
nipponium, after
Japan (which is Nippon in Japanese). In 2004, H. K Yoshihara used “a record of X-ray spectrum of Ogawa’s nipponium sample from thorianite [which] was contained in a photographic plate preserved by his family. The spectrum was read and indicated the absence of the element 43 and the presence of the element 75 (
rhenium).”
[5]
German chemists
Walter Noddack,
Otto Berg, and
Ida Tacke 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).
[6] The group bombarded
columbite with a beam of
electrons and deduced element 43 was present by examining
X-ray diffraction
spectrograms.
[7] The
wavelength of the X-rays produced is related to the atomic number by a formula 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 for many years.
[8][9] Still, in 1933, a series of articles on the discovery of elements quoted the namemasurium for element 43.
[10][note 1] Debate still exists as to whether the 1925 team actually did discover element 43.
[11]
Official discovery and later history
Segrè enlisted his colleague Perrier to attempt to prove, through comparative chemistry, that the molybdenum activity was indeed from an element with
Z = 43. They succeeded in isolating the
isotopes technetium-95m and
technetium-97.
[13][14] University of Palermo officials wanted them to name their discovery “panormium”, after the
Latin name for
Palermo, Panormus. In 1947
[13] element 43 was named after the
Greek word τεχνητός, meaning “artificial”, since it was the first element to be artificially produced.
[4][6] Segrè returned to Berkeley and met
Glenn T. Seaborg. They isolated the
metastable isotope technetium-99m, which is now used in some ten million medical diagnostic procedures annually.
[15]
Physical properties
Chemical properties
Technetium is placed in the
seventh group of the periodic table, between
rhenium and
manganese. As predicted by the
periodic law, its chemical properties are therefore intermediate between those two elements. Of the two, technetium more closely resembles rhenium, particularly in its chemical inertness and tendency to form
covalent bonds.
[23] Unlike manganese, technetium does not readily form
cations (
ions with a net positive charge). Common
oxidation states of technetium include +4, +5, and +7.
[24] Technetium dissolves in
aqua regia,
nitric acid, and concentrated
sulfuric acid, but it is not soluble in
hydrochloric acidof any concentration.
[18]
Hydride and oxides
The reaction of technetium with
hydrogen produces the negatively charged
hydride TcH2−9 ion, which has the same type of
crystal structure as (is isostructural with)
ReH2−9. It consists of a trigonal prism with a technetium atom in the center and six
hydrogen atoms at the corners. Three more hydrogen atoms make a triangle lying parallel to the base and crossing the prism in its center. Although those hydrogen atoms are not equivalent geometrically, their electronic structure is almost the same. This complex has a
coordination number of 9 (meaning that the technetium atom has nine neighbors), which is the highest for a technetium complex. Two hydrogen atoms in the complex can be replaced by sodium (Na+) or potassium (K+) ions.
[25]

Technetium hydride
Metallic technetium slowly
tarnishes in moist air,
[24] and in powder form, will burn in
oxygen. Two
oxides have been observed: TcO2and Tc2O7. Under
oxidizing conditions, which tend to strip electrons from atoms, technetium(VII) will exist as the
pertechnetate ion, TcO−
At temperatures of 400–450 °C, technetium oxidizes to form the pale-yellow
heptoxide:4 Tc + 7 O2 → 2 Tc2O7
This compound adopts a
centrosymmetric structure with two types of Tc-O bonds; their bond lengths are 167 and 184 pm, and the O-Tc-O angle is 180°.
[26]
Black-colored technetium dioxide (TcO2) can be produced by reduction of heptoxide with technetium or hydrogen.
[28]
Pertechnetic acid (HTcO4) is produced by reacting Tc2O7 with water or
oxidizing acids, such as
nitric acid, concentrated sulfuric acid,
aqua regia, or a mixture of nitric and hydrochloric acids.
[29] The resulting dark red,
hygroscopic (water absorbing) substance is a strong acid and easily donates protons. In concentrated
sulfuric acid Tc(VII) tetraoxidotechnetate anion converts to the octahedral form of technetic(VII) acid TcO3(OH)(H2O)2.
[30]
4 consists of a
tetrahedron with oxygens in the corners and a technetium atom in the center. Unlike
permanganate (MnO−
4), it is only a weak oxidizing agent. Pertechnate is often used as a convenient water-soluble source of technetium isotopes, such as 99mTc, and as a
catalyst.
[31]
Sulfides, selenides, and tellurides
Technetium forms various
sulfides. TcS2 is obtained by direct reaction of technetium and elemental
sulfur, while Tc2S7 is formed from the pertechnic acid as follows:2 HTcO4 + 7 H2S → Tc2S7 + 8 H2O
In this reaction technetium is
reduced to Tc(IV) while excess sulfur forms a disulfide ligand. The produced technetium heptasulfide has a polymeric structure (Tc3(µ3–S)(S2)3S6)n with a core similar to Mo3(µ3–S)(S2)62–.
[32]
Upon heating, technetium heptasulfide decomposes into disulfide and elementary sulfur:Tc2S7 → 2 TcS2 + 3 S

Technetium clusters Tc6 and Tc8
Technetium carbide and orthorhombic technetium metal phase
When small amounts of carbon are present in technetium metal, its ideal close-packed hexagonal crystal structure is distorted to orthorhombic technetium metal structure. Higher content of carbon (starting from 15-17% at.) provide complete conversion of technetium metal to cubic technetium carbide with approximate composition of Tc6C. The further increase in carbon content does not provide any change in technetium carbide structure.
[34]
Several technetium clusters are known, including Tc4, Tc6, Tc8 and Tc13.
[35][36] 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 halogen atoms such as
chlorine or
bromine.
[37]

Organic complex of technetium.
[38]
Technetium forms numerous organic complexes, which are relatively well-investigated because of their importance for nuclear medicine. Technetium carbonyl (Tc2(CO)10) is a white solid.
[39] In this molecule, two technetium atoms are weakly bound to each other; each atom is surrounded by
octahedra of five carbonyl ligands. The bond length between technetium atoms, 303 pm,
[40][41]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.
[42]
A technetium complex
[note 3] with an organic ligand (shown in the figure on right) is commonly used in nuclear medicine. It has a unique Tc-O
functional group (moiety) oriented perpendicularly to the plane of the molecule, where the oxygen atom can be replaced by a nitrogen atom.
[43]
Technetium, with
atomic number (denoted Z) 43, is the lowest-numbered element in the periodic table that is exclusively
radioactive. The second-lightest, exclusively radioactive element,
promethium, has an atomic number of 61.
[24] Atomic nuclei with an odd number of
protons are less stable than those with even numbers, even when the total number of
nucleons(protons +
neutrons) are even.
[44] Odd numbered elements therefore have fewer stable
isotopes.
The most stable
radioactive isotopes are technetium-98 with a
half-life of 4.2 million years (
Ma), technetium-97 (half-life: 2.6 million years and technetium-99 (half-life: 211,000 years).
[45]
Thirty other radioisotopes have been characterized with
mass numbers ranging from 85 to 118.
[45]Most of these have half-lives that are less than an hour; the exceptions are technetium-93 (half-life: 2.73 hours), technetium-94 (half-life: 4.88 hours), technetium-95 (half-life: 20 hours), and technetium-96 (half-life: 4.3 days).
[46]
Technetium also has numerous
nuclear isomers, which are isotopes with one or more
excitednucleons. Technetium-97m (97mTc; ‘m’ stands for
metastability) is the most stable, with a half-life of 91 days (0.0965 MeV).
[46] This is followed by technetium-95m (half-life: 61 days, 0.03 MeV), and technetium-99m (half-life: 6.01 hours, 0.142 MeV).
[46] Technetium-99m only emits
gamma rays and decays to technetium-99.
[46]
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 a second (that is, 0.62 G
Bq/g).
[20]
Occurrence and production

Uranium ores contain traces of technetium
Only minute traces occur naturally in the Earth’s
crust as a spontaneous
fission product in
uranium ores. A kilogram of uranium contains an estimated 1 nanogram (10−9 g) of technetium.
[14][48][49]Some
red giant stars with the spectral types S-, M-, and N contain an absorption line in their spectrum indicating the presence of technetium.
[18][50] These red-giants are known informally as
technetium stars.
[
edit]Fission waste product
Other
fissile isotopes also produce similar yields of technetium, such as 4.9% from
uranium-233 and 6.21% from
plutonium-239.
[51] About 49,000 T
Bq (78
metric tons) of technetium is estimated to have been produced in nuclear reactors between 1983 and 1994, which is by far the dominant source of terrestrial technetium.
[52][53]
Technetium-99 is produced by the
nuclear fission 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 dominant after about 104 to 106 years after the creation of the nuclear waste.
[52]
From 1945 to 1994, an estimated 160 T
Bq(about 250 kg) of technetium-99 was released into the environment by atmospheric
nuclear tests.
[52][54]
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 plant, which released an estimated 550 TBq (about 900 kg) from 1995–1999 into the
Irish Sea.
[53]
From 2000 onwards the amount has been limited by regulation to 90 TBq (about 140 kg) per year.
[55] Discharge of technetium into the sea has resulted in some seafood containing minuscule quantities of this element. For example,
European lobster and fish from west
Cumbria contain about 1 Bq/kg of technetium.
[56][57][note 5]
Fission product for commercial use
The
metastable isotope technetium-99m is continuously produced as a
fission product from the fission of uranium or
plutonium in
nuclear reactors. Because used fuel is allowed to stand for several years before reprocessing, all molybdenum-99 and technetium-99m will have decayed by the time that the fission products are separated from the major
actinides in conventional
nuclear reprocessing. The liquid left after plutonium–uranium extraction (
PUREX) contains a high concentration of technetium as TcO−4 but almost all of this is technetium-99, not technetium-99m.
[58]
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,
[59] and recovering at the diagnostic center the technetium-99m that is produced upon decay of molybdenum-99.
[60][61] Molybdenum-99 in the form of molybdate MoO2−4 is
adsorbed onto acid alumina (Al2O3) in a
shielded column chromatographinside 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.
[14] The soluble
pertechnetate TcO−4 can then be chemically extracted by
elution using a
saline solution.
By irradiating a highly enriched uranium target to produce molybdenum-99, there is no need for the complex chemical steps which would be required to separate molybdenum from a fission product mixture. A drawback of this process is that it requires targets containing uranium-235, which are subject to the security precautions of fissile materials.
[62][63]
All major technetium-99m producing reactors were built in the 1960s and are close to the end of their lifetime. The two new Canadian
Multipurpose Applied Physics Lattice Experiment reactors planned and built to produce 200% of the demand of technetium-99m relieved all other producers from building their own reactors. With the cancellation of the already tested reactors in 2008 the future supply of technetium-99m became very problematic.
[64]
However the Chalk River reactor has been shut down for maintenance since August 2009, with an expected reopening in April 2010, and the Petten reactor had a 6-month scheduled maintenance shutdown beginning on Friday, February 19, 2010. With millions of procedures relying on technetium-99m every year, the low supply has left a gap, leaving some practitioners to revert to techniques not used for 20 years. Somewhat allaying this issue is an announcement from the Polish
Maria research reactor that they have developed a technique to isolate technetium.
[65] The reactor at Chalk River Laboratory reopened in August 2010 and the Petten reactor reopened September 2010.
[66]
Waste disposal
The long half-life of technetium-99 and its ability to form an
anionic species makes it a major concern for long-term disposal of radioactive waste. Many of the processes designed to remove fission products in reprocessing plants aim at
cationic species like
caesium (e.g.,
caesium-137) and
strontium (e.g.,
strontium-90). Hence the pertechnetate is able to escape through these treatment processes. Current disposal options favor
burial in continental, geologically stable rock. The primary danger with such a course is that the waste is likely to come into contact with water, which could leach radioactive contamination into the environment. The anionic pertechnetate and
iodide do not adsorb well onto the surfaces of minerals, so they are likely to be washed away. By comparison
plutonium,
uranium, and
caesium are much more able to bind to soil particles. Technetium could also be immobilized by some environments, such as lake bottom sediments, due to microbial activity;
[67] for this reason, the environmental chemistry of technetium is an active area of research.
[68]
An alternative disposal method,
transmutation, has been demonstrated at
CERN for technetium-99. This transmutation process is one in which 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
ruthenium-100. If recovery of usable ruthenium is a goal, an extremely pure technetium target is needed; if small traces of the
minor actinidessuch as
americium and
curium are present in the target, they are likely to undergo fission and form more
fission products which increase the radioactivity of the irradiated target. The formation of ruthenium-106 (half-life 374 days) from the ‘fresh fission’ is likely to increase the activity of the final ruthenium metal, which will then require a longer cooling time after irradiation before the ruthenium can be used.
[69]
The actual separation of technetium-99 from spent nuclear fuel is a long process. During
fuel reprocessing, it appears in the waste liquid, which is highly radioactive. After sitting for several years, the radioactivity falls to a point where extraction of the long-lived isotopes, including technetium-99, becomes feasible. Several chemical extraction processes are then used, yielding technetium-99 metal of high purity.
[70]
Neutron activation
Molybdenum-99 can be formed by the
neutron activation of molybdenum-98.
[71] Other technetium isotopes are not produced in significant quantities by fission; when needed, they are manufactured by neutron irradiation of parent isotopes (for example, technetium-97 can be made by neutron irradiation of ruthenium-96).
[72]
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.
[73] The recent shortages of medical technetium-99m reignited the interest in its production by proton bombardment of isotopically-enriched (>99.5%) molybdenum-100 targets.
[74] Other particle accelerator-based isotope production techniques have been investigated to obtain molybdenum-99 from molybdenum-100 via (n,2n) or (γ,n) reactions.
[75][76][77]
Nuclear medicine and biology
Technetium-99m (“m” indicates that this is a
metastable nuclear isomer) is used in radioactive isotope
medical tests, for example as a
radioactive tracer that medical equipment can detect in the human body.
[14] 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).
[20]
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.
[79]
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 therefore used for equipment calibration.
[80] Technetium-99 has also been proposed for use in optoelectronic devices and
nanoscale nuclear batteries.
[81]
When steel is immersed in water, adding a small concentration (55
ppm) of potassium pertechnetate(VII) to the water protects the
steel from corrosion, even if the temperature is raised to 250 °C.
[83] For this reason, pertechnetate has been used as a possible anodic
corrosion inhibitor for steel, although technetium’s radioactivity poses problems which limit this application to self-contained systems.
[84] While (for example) CrO2− 4 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.
[83]The mechanism by which pertechnetate prevents corrosion is not well understood, but seems to involve the reversible formation of a thin surface layer. One theory holds that the pertechnetate reacts with the steel surface to form a layer of technetium
dioxide which prevents further corrosion; the same effect explains how iron powder can be used to remove pertechnetate from water. (
Activated carbon can also be used for the same effect.) 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.
[85]
As noted, the radioactive nature of technetium (3 M
Bq per liter 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.
[85]
Precautions
Technetium plays no natural biological role and is not normally found in the human body.
[18]Technetium is produced in quantity by nuclear fission, and spreads more readily than many radionuclides.
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.”
According to the EPA: “Technetium is an oddity in the middle of the Periodic Table; it has no stable isotopes. Any primordial technetium has decayed away because its longest-lived isotope, 98Tc, has a half-life of only 4.2 ×106 years. The most significant isotope produced as a result of nuclear fission, 99Tc, has a half-life of 2.1 × 105 years. It decays by emission of a beta particle (Eβmax= 0.29 MeV). In the environment, very small quantities of this isotope can be ascribed to the natural fission process of uranium ores.
Technetium-99 is the most significant technetium isotope present in wastes from nuclear power plants, especially in spent fuel. Medical wastes are an additional source of 99 Tc, because 99m Tc (the“m” is for “metastable”) is used as a radio-imaging isotope for oncological assessments. The isomeric isotope 99m Tc has a half-life of only six hours, and decays directly to the ground state, 99 Tc through gamma emission. The chemistry of technetium is very similar to that of rhenium. The most common oxidation states of technetium are (+4) and (VII). In an oxidative environment, technetium will be present as the pertechnetate ion, TcO–4, which has significant mobility in ground water (i.e., not well retained bysoils). In reducing environments, technetium will form partially soluble TcO2.
Technetium forms complexes with organic and inorganic ligands under many different conditions and can be easily separated from other radionuclides using ion chromatography. Radiochemical analysis for 99Tc can be performed by GPC, using the gamma emitter 99m Tc (t½ . 6 h) to monitor yield. In ICP-MS and some gravimetric analyses, rhenium is used as a yield monitor for technetium.
http://www.epa.gov/narel/IRM_Final.pdf
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This is the best reporting on Tc99, also the companion article at 'Tons of Radioactive'. Thanks and best to you.
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