Thulium
Encyclopedia
Thulium is a chemical element
that has the symbol Tm and atomic number
69. Thulium is the second least abundant of the lanthanides (promethium
is only found in trace quantities
on Earth). It is an easily workable metal
with a bright silvery-gray luster. Despite its high price and rarity, thulium is used as the radiation source in portable X-ray
devices and in solid-state laser
s.
to form thulium(III) oxide
:
Thulium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form thulium hydroxide:
Thulium reacts with all the halogens. Reactions are slow at room temperature, but are vigorous above 200 °C:
Thulium dissolves readily in dilute sulfuric acid
to form solutions containing the pale green Tm(III) ions, which exist as a [Tm(OH2)9]3+ complexes:
Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including TmN, TmS, TmC2, Tm2C3, TmH2, TmH3, TmSi2, TmGe3, TmB4, TmB6 and TmB12. In those compounds, thulium exhibits valence states +2, +3 and +4, however, the +3 state is most common and only this state has been observed in Tm solutions.
, Tm-169 (100% natural abundance
). Thirty one radioisotopes have been characterized, with the most stable being Tm-171 with a half-life
of 1.92 years, Tm-170 with a half-life of 128.6 days, Tm-168 with a half-life of 93.1 days, and Tm-167 with a half-life of 9.25 days. All of the remaining radioactive isotopes have half-lives that are less than 64 hours, and the majority of these have half-lives that are less than 2 minutes. This element also has 14 meta states, with the most stable being Tm-164m (t½ 5.1 minutes), Tm-160m (t½ 74.5 seconds) and Tm-155m (t½ 45 seconds).
The isotopes of thulium range in atomic weight
from 145.966 u
(Tm-146) to 176.949 u (Tm-177). The primary decay mode before the most abundant stable isotope, Tm-169, is electron capture
, and the primary mode after is beta emission. The primary decay product
s before Tm-169 are element 68 (erbium
) isotopes, and the primary products after are element 70 (ytterbium
) isotopes.
in 1879 by looking for impurities in the oxide
s of other rare earth elements (this was the same method Carl Gustaf Mosander
earlier used to discover some other rare earth elements). Cleve started by removing all of the known contaminants of erbia (Er
2O
3). Upon additional processing, he obtained two new substances; one brown and one green. The brown substance was the oxide of the element holmium
and was named holmia by Cleve, and the green substance was the oxide of an unknown element. Cleve named the oxide thulia and its element thulium after Thule
, Scandinavia.
Thulium was so rare that none of the early workers had enough of it to purify sufficiently to actually see the green color; they had to be content with spectroscopically
observing the strengthening of the two characteristic absorption bands, as erbium was progressively removed. The first researcher to obtain nearly pure thulium was Charles James, a British expatriate working on a large scale at New Hampshire College
in Durham
. In 1911 he reported his results, having used his discovered method of bromate fractional crystallization to do the purification. He famously needed 15,000 "operations" to establish that the material was homogeneous.
High-purity thulium oxide was first offered commercially in the late 1950s, as a result of the adoption of ion-exchange separation technology. Lindsay Chemical Division of American Potash & Chemical Corporation offered it in grades of 99% and 99.9% purity. The price per kilogram has oscillated between US$ 4,600 and $13,300 in the period from 1959 to 1998 for 99.9% purity, and it was second highest for lanthanides behind lutetium.
The element is never found in nature in pure form, but it is found in small quantities in mineral
s with other rare earths. Its abundance in the Earth crust is 0.5 mg/kg. Thulium is principally extracted from monazite
(~0.007% thulium) ores found in river sands, through ion-exchange. Newer ion-exchange and solvent-extraction techniques have led to easier separation of the rare earths, which has yielded much lower costs for thulium production. The principal sources today are the ion adsorption clays of southern China. In these, where about two-thirds of the total rare-earth content is yttrium, thulium is about 0.5% (or about tied with lutetium for rarity). The metal can be isolated through reduction
of its oxide with lanthanum
metal or by calcium
reduction in a closed container. None of thulium's natural compounds are commercially important.
-chromium
-thulium triple-doped YAG (Ho:Cr:Tm:YAG, or Ho,Cr,Tm:YAG) is an active laser medium material with high efficiency. It lases at 2097 nm and is widely used in military, medicine, and meteorology. Single-element thulium-doped YAG (Tm:YAG) lasers operate between 1930 and 2040 nm. The wavelength of thulium-based lasers is very efficient for superficial ablation of tissue, with minimal coagulation depth in air or in water. This makes thulium lasers attractive for laser-based surgery.
as a radiation source. These sources are available for about one year, as tools in medical and dental diagnosis, as well as to detect defects in inaccessible mechanical and electronic components. Such sources do not need extensive radiation protection – only a small cup of lead.
. Thulium potentially has use in ferrite
s, ceramic magnetic materials that are used in microwave
equipment.
Chemical element
A chemical element is a pure chemical substance consisting of one type of atom distinguished by its atomic number, which is the number of protons in its nucleus. Familiar examples of elements include carbon, oxygen, aluminum, iron, copper, gold, mercury, and lead.As of November 2011, 118 elements...
that has the symbol Tm and atomic number
Atomic number
In chemistry and physics, the atomic number is the number of protons found in the nucleus of an atom and therefore identical to the charge number of the nucleus. It is conventionally represented by the symbol Z. The atomic number uniquely identifies a chemical element...
69. Thulium is the second least abundant of the lanthanides (promethium
Promethium
Promethium is a chemical element with the symbol Pm and atomic number 61. It is notable for being the only exclusively radioactive element besides technetium that is followed by chemical elements with stable isotopes.- Prediction :...
is only found in trace quantities
Trace radioisotope
A trace radioisotope is a radioisotope that occurs naturally in trace amounts . Generally speaking, trace radioisotopes have half-lives that are short in comparison to the age of the earth, since primordial nuclides tend to occur in larger than trace amounts...
on Earth). It is an easily workable metal
Metal
A metal , is an element, compound, or alloy that is a good conductor of both electricity and heat. Metals are usually malleable and shiny, that is they reflect most of incident light...
with a bright silvery-gray luster. Despite its high price and rarity, thulium is used as the radiation source in portable X-ray
X-ray
X-radiation is a form of electromagnetic radiation. X-rays have a wavelength in the range of 0.01 to 10 nanometers, corresponding to frequencies in the range 30 petahertz to 30 exahertz and energies in the range 120 eV to 120 keV. They are shorter in wavelength than UV rays and longer than gamma...
devices and in solid-state laser
Solid-state laser
A solid-state laser is a laser that uses a gain medium that is a solid, rather than a liquid such as in dye lasers or a gas as in gas lasers. Semiconductor-based lasers are also in the solid state, but are generally considered as a separate class from solid-state lasers .-Solid-state...
s.
Physical properties
Pure thulium metal has a bright, silvery luster. It is reasonably stable in air, but should be protected from moisture. The metal is soft, malleable, and ductile. Thulium is ferromagnetic below 32 K, antiferromagnetic between 32 and 56 K and paramagnetic above 56 K.Chemical properties
Thulium metal tarnishes slowly in air and burns readily at 150 °CCelsius
Celsius is a scale and unit of measurement for temperature. It is named after the Swedish astronomer Anders Celsius , who developed a similar temperature scale two years before his death...
to form thulium(III) oxide
Thulium(III) oxide
Thulium oxide is a pale green solid compound, with the formula Tm2O3. It was first isolated in 1878 from an impure sample of erbia by Per Teodor Cleve, who named it thulia....
:
- 4 Tm + 3 O2 → 2 Tm2O3
Thulium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form thulium hydroxide:
- 2 Tm (s) + 6 H2O (l) → 2 Tm(OH)3 (aq) + 3 H2 (g)
Thulium reacts with all the halogens. Reactions are slow at room temperature, but are vigorous above 200 °C:
- 2 Tm (s) + 3 F2 (g) → 2 TmF3 (s) [white]
- 2 Tm (s) + 3 Cl2 (g) → 2 TmCl3 (s) [yellow]
- 2 Tm (s) + 3 Br2 (g) → 2 TmBr3 (s) [white]
- 2 Tm (s) + 3 I2 (g) → 2 TmI3 (s) [yellow]
Thulium dissolves readily in dilute sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...
to form solutions containing the pale green Tm(III) ions, which exist as a [Tm(OH2)9]3+ complexes:
- 2 Tm (s) + 3 H2SO4 (aq) → 2 Tm3+ (aq) + 3 (aq) + 3 H2 (g)
Thulium reacts with various metallic and non-metallic elements forming a range of binary compounds, including TmN, TmS, TmC2, Tm2C3, TmH2, TmH3, TmSi2, TmGe3, TmB4, TmB6 and TmB12. In those compounds, thulium exhibits valence states +2, +3 and +4, however, the +3 state is most common and only this state has been observed in Tm solutions.
Isotopes
Naturally occurring thulium is composed of one stable isotopeIsotope
Isotopes are variants of atoms of a particular chemical element, which have differing numbers of neutrons. Atoms of a particular element by definition must contain the same number of protons but may have a distinct number of neutrons which differs from atom to atom, without changing the designation...
, Tm-169 (100% natural abundance
Natural abundance
In chemistry, natural abundance refers to the abundance of isotopes of a chemical element as naturally found on a planet. The relative atomic mass of these isotopes is the atomic weight listed for the element in the periodic table...
). Thirty one radioisotopes have been characterized, with the most stable being Tm-171 with a half-life
Half-life
Half-life, abbreviated t½, is the period of time it takes for the amount of a substance undergoing decay to decrease by half. The name was originally used to describe a characteristic of unstable atoms , but it may apply to any quantity which follows a set-rate decay.The original term, dating to...
of 1.92 years, Tm-170 with a half-life of 128.6 days, Tm-168 with a half-life of 93.1 days, and Tm-167 with a half-life of 9.25 days. All of the remaining radioactive isotopes have half-lives that are less than 64 hours, and the majority of these have half-lives that are less than 2 minutes. This element also has 14 meta states, with the most stable being Tm-164m (t½ 5.1 minutes), Tm-160m (t½ 74.5 seconds) and Tm-155m (t½ 45 seconds).
The isotopes of thulium range in atomic weight
Atomic weight
Atomic weight is a dimensionless physical quantity, the ratio of the average mass of atoms of an element to 1/12 of the mass of an atom of carbon-12...
from 145.966 u
Atomic mass unit
The unified atomic mass unit or dalton is a unit that is used for indicating mass on an atomic or molecular scale. It is defined as one twelfth of the rest mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state, and has a value of...
(Tm-146) to 176.949 u (Tm-177). The primary decay mode before the most abundant stable isotope, Tm-169, is electron capture
Electron capture
Electron capture is a process in which a proton-rich nuclide absorbs an inner atomic electron and simultaneously emits a neutrino...
, and the primary mode after is beta emission. The primary decay product
Decay product
In nuclear physics, a decay product is the remaining nuclide left over from radioactive decay. Radioactive decay often involves a sequence of steps...
s before Tm-169 are element 68 (erbium
Erbium
Erbium is a chemical element in the lanthanide series, with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements on Earth...
) isotopes, and the primary products after are element 70 (ytterbium
Ytterbium
Ytterbium is a chemical element with the symbol Yb and atomic number 70. A soft silvery metallic element, ytterbium is a rare earth element of the lanthanide series and is found in the minerals gadolinite, monazite, and xenotime. The element is sometimes associated with yttrium or other related...
) isotopes.
History
Thulium was discovered by Swedish chemist Per Teodor ClevePer Teodor Cleve
Per Teodor Cleve was a Swedish chemist and geologist.After graduating from the Stockholm Gymnasium in 1858, Cleve matriculated at Uppsala University in May 1858, where he received his PhD in 1863...
in 1879 by looking for impurities in the oxide
Oxide
An oxide is a chemical compound that contains at least one oxygen atom in its chemical formula. Metal oxides typically contain an anion of oxygen in the oxidation state of −2....
s of other rare earth elements (this was the same method Carl Gustaf Mosander
Carl Gustaf Mosander
Carl Gustaf Mosander was a Swedish chemist. He discovered the elements lanthanum, erbium and terbium....
earlier used to discover some other rare earth elements). Cleve started by removing all of the known contaminants of erbia (Er
Erbium
Erbium is a chemical element in the lanthanide series, with the symbol Er and atomic number 68. A silvery-white solid metal when artificially isolated, natural erbium is always found in chemical combination with other elements on Earth...
2O
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
3). Upon additional processing, he obtained two new substances; one brown and one green. The brown substance was the oxide of the element holmium
Holmium
Holmium is a chemical element with the symbol Ho and atomic number 67. Part of the lanthanide series, holmium is a rare earth element. Its oxide was first isolated from rare earth ores in 1878 and the element was named after the city of Stockholm....
and was named holmia by Cleve, and the green substance was the oxide of an unknown element. Cleve named the oxide thulia and its element thulium after Thule
Thule
Thule Greek: Θούλη, Thoulē), also spelled Thula, Thila, or Thyïlea, is, in classical European literature and maps, a region in the far north. Though often considered to be an island in antiquity, modern interpretations of what was meant by Thule often identify it as Norway. Other interpretations...
, Scandinavia.
Thulium was so rare that none of the early workers had enough of it to purify sufficiently to actually see the green color; they had to be content with spectroscopically
Spectroscopy
Spectroscopy is the study of the interaction between matter and radiated energy. Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, e.g., by a prism. Later the concept was expanded greatly to comprise any interaction with radiative...
observing the strengthening of the two characteristic absorption bands, as erbium was progressively removed. The first researcher to obtain nearly pure thulium was Charles James, a British expatriate working on a large scale at New Hampshire College
University of New Hampshire
The University of New Hampshire is a public university in the University System of New Hampshire , United States. The main campus is in Durham, New Hampshire. An additional campus is located in Manchester. With over 15,000 students, UNH is the largest university in New Hampshire. The university is...
in Durham
Durham, New Hampshire
As of the census of 2000, there were 12,664 people, 2,882 households, and 1,582 families residing in the town. The population density was 565.5 people per square mile . There were 2,923 housing units at an average density of 130.5 per square mile...
. In 1911 he reported his results, having used his discovered method of bromate fractional crystallization to do the purification. He famously needed 15,000 "operations" to establish that the material was homogeneous.
High-purity thulium oxide was first offered commercially in the late 1950s, as a result of the adoption of ion-exchange separation technology. Lindsay Chemical Division of American Potash & Chemical Corporation offered it in grades of 99% and 99.9% purity. The price per kilogram has oscillated between US$ 4,600 and $13,300 in the period from 1959 to 1998 for 99.9% purity, and it was second highest for lanthanides behind lutetium.
Occurrence and production
The element is never found in nature in pure form, but it is found in small quantities in mineral
Mineral
A mineral is a naturally occurring solid chemical substance formed through biogeochemical processes, having characteristic chemical composition, highly ordered atomic structure, and specific physical properties. By comparison, a rock is an aggregate of minerals and/or mineraloids and does not...
s with other rare earths. Its abundance in the Earth crust is 0.5 mg/kg. Thulium is principally extracted from monazite
Monazite
Monazite is a reddish-brown phosphate mineral containing rare earth metals. It occurs usually in small isolated crystals. There are actually at least four different kinds of monazite, depending on relative elemental composition of the mineral:...
(~0.007% thulium) ores found in river sands, through ion-exchange. Newer ion-exchange and solvent-extraction techniques have led to easier separation of the rare earths, which has yielded much lower costs for thulium production. The principal sources today are the ion adsorption clays of southern China. In these, where about two-thirds of the total rare-earth content is yttrium, thulium is about 0.5% (or about tied with lutetium for rarity). The metal can be isolated through reduction
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
of its oxide with lanthanum
Lanthanum
Lanthanum is a chemical element with the symbol La and atomic number 57.Lanthanum is a silvery white metallic element that belongs to group 3 of the periodic table and is the first element of the lanthanide series. It is found in some rare-earth minerals, usually in combination with cerium and...
metal or by calcium
Calcium
Calcium is the chemical element with the symbol Ca and atomic number 20. It has an atomic mass of 40.078 amu. Calcium is a soft gray alkaline earth metal, and is the fifth-most-abundant element by mass in the Earth's crust...
reduction in a closed container. None of thulium's natural compounds are commercially important.
Laser
HolmiumHolmium
Holmium is a chemical element with the symbol Ho and atomic number 67. Part of the lanthanide series, holmium is a rare earth element. Its oxide was first isolated from rare earth ores in 1878 and the element was named after the city of Stockholm....
-chromium
Chromium
Chromium is a chemical element which has the symbol Cr and atomic number 24. It is the first element in Group 6. It is a steely-gray, lustrous, hard metal that takes a high polish and has a high melting point. It is also odorless, tasteless, and malleable...
-thulium triple-doped YAG (Ho:Cr:Tm:YAG, or Ho,Cr,Tm:YAG) is an active laser medium material with high efficiency. It lases at 2097 nm and is widely used in military, medicine, and meteorology. Single-element thulium-doped YAG (Tm:YAG) lasers operate between 1930 and 2040 nm. The wavelength of thulium-based lasers is very efficient for superficial ablation of tissue, with minimal coagulation depth in air or in water. This makes thulium lasers attractive for laser-based surgery.
X-ray source
Despite its high cost, portable X-ray devices use thulium that has been bombarded in a nuclear reactorNuclear reactor
A nuclear reactor is a device to initiate and control a sustained nuclear chain reaction. Most commonly they are used for generating electricity and for the propulsion of ships. Usually heat from nuclear fission is passed to a working fluid , which runs through turbines that power either ship's...
as a radiation source. These sources are available for about one year, as tools in medical and dental diagnosis, as well as to detect defects in inaccessible mechanical and electronic components. Such sources do not need extensive radiation protection – only a small cup of lead.
Others
Thulium has been used in high temperature superconductors similarly to yttriumYttrium
Yttrium is a chemical element with symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and it has often been classified as a "rare earth element". Yttrium is almost always found combined with the lanthanides in rare earth minerals and is...
. Thulium potentially has use in ferrite
Ferrite (magnet)
Ferrites are chemical compounds consisting of ceramic materials with iron oxide as their principal component. Many of them are magnetic materials and they are used to make permanent magnets, ferrite cores for transformers, and in various other applications.Many ferrites are spinels with the...
s, ceramic magnetic materials that are used in microwave
Microwave
Microwaves, a subset of radio waves, have wavelengths ranging from as long as one meter to as short as one millimeter, or equivalently, with frequencies between 300 MHz and 300 GHz. This broad definition includes both UHF and EHF , and various sources use different boundaries...
equipment.
Biological role and precautions
Thulium has no known biological role, although it has been noted that it stimulates metabolism. Soluble thulium salts are regarded as slightly toxic if taken in large amounts, but the insoluble salts are non-toxic. Thulium is not taken up by plant roots to any extent and thus does not get into the human food chain. Vegetables typically contain only one milligram of thulium per tonne (dry weight).External links
- WebElements.com – Thulium (also used as a reference)
- It's Elemental – Thulium