|Pronunciation|| / /|
|Standard atomic weight Ar, std(Tm)||168.934218(6)|
|Thulium in the periodic table|
|Atomic number (Z)||69|
|Electron configuration||[ Xe ] 4f13 6s2|
|Electrons per shell||2, 8, 18, 31, 8, 2|
|Phase at STP||solid|
|Melting point||1818 K (1545 °C,2813 °F)|
|Boiling point||2223 K(1950 °C,3542 °F)|
|Density (near r.t.)||9.32 g/cm3|
|when liquid (at m.p.)||8.56 g/cm3|
|Heat of fusion||16.84 kJ/mol|
|Heat of vaporization||191 kJ/mol|
|Molar heat capacity||27.03 J/(mol·K)|
| Vapor pressure |
|Oxidation states||0, +2, +3 (a basic oxide)|
|Electronegativity||Pauling scale: 1.25|
|Atomic radius||empirical:176 pm|
|Covalent radius||190±10 pm|
|Spectral lines of thulium|
|Crystal structure|| hexagonal close-packed (hcp)|
|Thermal expansion||poly: 13.3 µm/(m·K)(at r.t.)|
|Thermal conductivity||16.9 W/(m·K)|
|Electrical resistivity||poly: 676 nΩ·m(at r.t.)|
|Magnetic ordering||paramagnetic (at 300 K)|
|Magnetic susceptibility||+25,500·10−6 cm3/mol(291 K)|
|Young's modulus||74.0 GPa|
|Shear modulus||30.5 GPa|
|Bulk modulus||44.5 GPa|
|Vickers hardness||470–650 MPa|
|Brinell hardness||470–900 MPa|
|Naming||after Thule, a mythical region in Scandinavia|
|Discovery and first isolation||Per Teodor Cleve (1879)|
|Main isotopes of thulium|
Thulium is a chemical element with the symbol Tm and atomic number 69. It is the thirteenth and third-last element in the lanthanide series. Like the other lanthanides, the most common oxidation state is +3, seen in its oxide, halides and other compounds; because it occurs so late in the series, however, the +2 oxidation state is also stabilized by the nearly full 4f shell that results. In aqueous solution, like compounds of other late lanthanides, soluble thulium compounds form coordination complexes with nine water molecules.
In 1879, the Swedish chemist Per Teodor Cleve separated from the rare earth oxide erbia another two previously unknown components, which he called holmia and thulia; these were the oxides of holmium and thulium, respectively. A relatively pure sample of thulium metal was first obtained in 1911.
Thulium is the second-least abundant of the lanthanides, after radioactively unstable promethium which is only found in trace quantities on Earth. It is an easily workable metal with a bright silvery-gray luster. It is fairly soft and slowly tarnishes in air. Despite its high price and rarity, thulium is used as the radiation source in portable X-ray devices, and in some solid-state lasers. It has no significant biological role and is not particularly toxic.
Pure thulium metal has a bright, silvery luster, which tarnishes on exposure to air. The metal can be cut with a knife, K, antiferromagnetic between 32 and 56 K, and paramagnetic above 56 K.as it has a Mohs hardness of 2 to 3; it is malleable and ductile. Thulium is ferromagnetic below 32
Thulium has two major allotropes: the tetragonal α-Tm and the more stable hexagonal β-Tm.
Thulium tarnishes slowly in air and burns readily at 150 °C 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 [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.[ citation needed ] In those compounds, thulium exhibits valence states +2 and +3, however, the +3 state is most common and only this state has been observed in thulium solutions. Thulium exists as a Tm3+ ion in solution. In this state, the thulium ion is surrounded by nine molecules of water. Tm3+ ions exhibit a bright blue luminescence.
Thulium's only known oxide is Tm2O3. This oxide is sometimes called "thulia". [ citation needed ] Combination of thulium and chalcogens results in thulium chalcogenides.Reddish-purple thulium(II) compounds can be made by the reduction of thulium(III) compounds. Examples of thulium(II) compounds include the halides (except the fluoride). Some hydrated thulium compounds, such as TmCl3·7H2O and Tm2(C2O4)3·6H2O are green or greenish-white. Thulium dichloride reacts very vigorously with water. This reaction results in hydrogen gas and Tm(OH)3 exhibiting a fading reddish color.
Thulium reacts with hydrogen chloride to produce hydrogen gas and thulium chloride. With nitric acid it yields thulium nitrate, or Tm(NO3)3.
The isotopes of thulium range from 145Tm to 179Tm. The primary decay mode before the most abundant stable isotope, 169Tm, is electron capture, and the primary mode after is beta emission. The primary decay products before 169Tm are element 68 (erbium) isotopes, and the primary products after are element 70 (ytterbium) isotopes.
Thulium-169 is thulium's only primordial isotope and is the only isotope of thulium that is thought to be stable; it is predicted to undergo alpha decay to holmium-165 with a very long half-life.The longest-lived radioisotopes are thulium-171, which has a half-life of 1.92 years, and thulium-170, which has a half-life of 128.6 days. Most other isotopes have half-lives of a few minutes or less. Thirty-five isotopes and 26 nuclear isomers of thulium have been detected. Most isotopes of thulium lighter than 169 atomic mass units decay via electron capture or beta-plus decay, although some exhibit significant alpha decay or proton emission. Heavier isotopes undergo beta-minus decay.
Thulium was discovered by Swedish chemist Per Teodor Cleve in 1879 by looking for impurities in the oxides 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 2 O 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, an Ancient Greek place name associated with Scandinavia or Iceland. Thulium's atomic symbol was once Tu, but this was changed to Tm.
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, USA. In 1911 he reported his results, having used his discovered method of bromate fractional crystallization to do the purification. He famously needed 15,000 purification 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 oscillated between US$4,600 and $13,300 in the period from 1959 to 1998 for 99.9% purity, and it was the second highest for the lanthanides behind lutetium.
The element is never found in nature in pure form, but it is found in small quantities in minerals with other rare earths. Thulium is often found with minerals containing yttrium and gadolinium. In particular, thulium occurs in the mineral gadolinite. mg/kg by weight and 50 parts per billion by moles. Thulium makes up approximately 0.5 parts per million of soil, although this value can range from 0.4 to 0.8 parts per million. Thulium makes up 250 parts per quadrillion of seawater. In the solar system, thulium exists in concentrations of 200 parts per trillion by weight and 1 part per trillion by moles. Thulium ore occurs most commonly in China. However, Australia, Brazil, Greenland, India, Tanzania, and the United States also have large reserves of thulium. Total reserves of thulium are approximately 100,000 tonnes. Thulium is the least abundant lanthanide on earth except for the radioactive promethium.However, thulium also occurs in the minerals monazite, xenotime, and euxenite. Thulium has not been found in prevalence over the other rare earths in any mineral yet. Its abundance in the Earth's crust is 0.5
Thulium is principally extracted from monazite ores (~0.007% thulium) 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. Approximately 50 tonnes per year of thulium oxide are produced.In 1996, thulium oxide cost US$20 per gram, and in 2005, 99%-pure thulium metal powder cost US$70 per gram.
Thulium has a few applications:
Holmium-chromium-thulium triple-doped yttrium aluminum garnet (Ho:Cr:Tm:YAG, or Ho,Cr,Tm:YAG) is an active laser medium material with high efficiency. It lases at 2080 nm in the Infra-Red and is widely used in military applications, medicine, and meteorology. Single-element thulium-doped YAG (Tm:YAG) lasers operate at 2010 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.
Despite its high cost, portable X-ray devices use thulium that has been bombarded with neutrons in a nuclear reactor to produce the isotope Thulium-170, having a half-life of 128.6 days and five major emission lines of comparable intensity (at 7.4, 51.354, 52.389, 59.4 and 84.253 keV).These radioactive sources have a useful life of 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. They are among the most popular radiation sources for use in industrial radiography. Thulium-170 is gaining popularity as an X-ray source for cancer treatment via brachytherapy (sealed source radiation therapy).
Thulium has been used in high-temperature superconductors similarly to yttrium. Thulium potentially has use in ferrites, ceramic magnetic materials that are used in microwave equipment.Thulium is also similar to scandium in that it is used in arc lighting for its unusual spectrum, in this case, its green emission lines, which are not covered by other elements. Because thulium fluoresces with a blue color when exposed to ultraviolet light, thulium is put into euro banknotes as a measure against counterfeiting. The blue fluorescence of Tm-doped calcium sulfate has been used in personal dosimeters for visual monitoring of radiation. Tm-doped halides in which Tm is in its 2+ valence state, are promising luminescent materials that can make efficient electricity generating windows based on the principle of a luminescent solar concentrator, possible.
Soluble thulium salts are mildly toxic, but insoluble thulium salts are completely nontoxic. [ citation needed ] In humans, thulium occurs in the highest amounts in the liver, kidneys, and bones. Humans typically consume several micrograms of thulium per year. The roots of plants do not take up thulium, and the dry weight of vegetables usually contains one part per billion of thulium. Thulium dust and powder are toxic upon inhalation or ingestion and can cause explosions.When injected, thulium can cause degeneration of the liver and spleen and can also cause hemoglobin concentration to fluctuate. Liver damage from thulium is more prevalent in male mice than female mice. Despite this, thulium has a low level of toxicity.
Dysprosium is a chemical element with the symbol Dy and atomic number 66. It is a rare-earth element with a metallic silver luster. Dysprosium is never found in nature as a free element, though it is found in various minerals, such as xenotime. Naturally occurring dysprosium is composed of seven isotopes, the most abundant of which is 164Dy.
Europium is a chemical element with the symbol Eu and atomic number 63. Europium is the most reactive lanthanide by far, having to be stored under an inert fluid to protect it from atmospheric oxygen or moisture. Europium is also the softest lanthanide, as it can be dented with a fingernail and easily cut with a knife. When oxidation is removed a shiny-white metal is visible. Europium was isolated in 1901 and is named after the continent of Europe. Being a typical member of the lanthanide series, europium usually assumes the oxidation state +3, but the oxidation state +2 is also common. All europium compounds with oxidation state +2 are slightly reducing. Europium has no significant biological role and is relatively non-toxic compared to other heavy metals. Most applications of europium exploit the phosphorescence of europium compounds. Europium is one of the rarest of the rare earth elements on Earth.
Erbium is a chemical element 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. It is a lanthanide, a rare earth element, originally found in the gadolinite mine in Ytterby in Sweden, from which it got its name.
Holmium is a chemical element with the symbol Ho and atomic number 67. Part of the lanthanide series, holmium is a rare-earth element.
Lanthanum is a chemical element with the symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air and is soft enough to be cut with a knife. It is the eponym of the lanthanide series, a group of 15 similar elements between lanthanum and lutetium in the periodic table, of which lanthanum is the first and the prototype. It is also sometimes considered the first element of the 6th-period transition metals, which would put it in group 3, although lutetium is sometimes placed in this position instead. Lanthanum is traditionally counted among the rare earth elements. The usual oxidation state is +3. Lanthanum has no biological role in humans but is essential to some bacteria. It is not particularly toxic to humans but does show some antimicrobial activity.
Lutetium is a chemical element with the symbol Lu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted among the rare earths. Lutetium is sometimes considered the first element of the 6th-period transition metals, although lanthanum is more often considered as such.
The lanthanide or lanthanoid series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yttrium, are often collectively known as the rare earth elements.
Neodymium is a chemical element with the symbol Nd and atomic number 60. Neodymium belongs to the lanthanide series and is a rare-earth element. It is a hard, slightly malleable silvery metal that quickly tarnishes in air and moisture. When oxidized, neodymium reacts quickly to produce pink, purple/blue and yellow compounds in the +2, +3 and +4 oxidation states. Neodymium was discovered in 1885 by the Austrian chemist Carl Auer von Welsbach. It is present in significant quantities in the ore minerals monazite and bastnäsite. Neodymium is not found naturally in metallic form or unmixed with other lanthanides, and it is usually refined for general use. Although neodymium is classed as a rare-earth element, it is fairly common, no rarer than cobalt, nickel, or copper, and is widely distributed in the Earth's crust. Most of the world's commercial neodymium is mined in China.
Scandium is a chemical element with the symbol Sc and atomic number 21. A silvery-white metallic d-block element, it has historically been classified as a rare-earth element, together with yttrium and the lanthanides. It was discovered in 1879 by spectral analysis of the minerals euxenite and gadolinite from Scandinavia.
Terbium is a chemical element with the symbol Tb and atomic number 65. It is a silvery-white, rare earth metal that is malleable, ductile, and soft enough to be cut with a knife. The ninth member of the lanthanide series, terbium is a fairly electropositive metal that reacts with water, evolving hydrogen gas. Terbium is never found in nature as a free element, but it is contained in many minerals, including cerite, gadolinite, monazite, xenotime, and euxenite.
Ytterbium is a chemical element with the symbol Yb and atomic number 70. It is the fourteenth and penultimate element in the lanthanide series, which is the basis of the relative stability of its +2 oxidation state. However, like the other lanthanides, its most common oxidation state is +3, as in its oxide, halides, and other compounds. In aqueous solution, like compounds of other late lanthanides, soluble ytterbium compounds form complexes with nine water molecules. Because of its closed-shell electron configuration, its density and melting and boiling points differ significantly from those of most other lanthanides.
Ytterby is a village on the Swedish island of Resarö, in Vaxholm Municipality in the Stockholm archipelago. Today the residential area is dominated by suburban homes.
The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The fifth period contains 18 elements, beginning with rubidium and ending with xenon. As a rule, period 5 elements fill their 5s shells first, then their 4d, and 5p shells, in that order; however, there are exceptions, such as rhodium.
Praseodymium is a chemical element with the symbol Pr and atomic number 59. It is the third member of the lanthanide series and is traditionally considered to be one of the rare-earth metals. Praseodymium is a soft, silvery, malleable and ductile metal, valued for its magnetic, electrical, chemical, and optical properties. It is too reactive to be found in native form, and pure praseodymium metal slowly develops a green oxide coating when exposed to air.
Per Teodor Cleve was a Swedish chemist, biologist, mineralogist and oceanographer. He is best known for his discovery of the chemical elements holmium and thulium.
Marc Delafontaine was a Swiss chemist and spectroscopist who was involved in discovering and investigating some of the rare earth elements.
Holmium(III) oxide, or holmium oxide is a chemical compound of a rare-earth element holmium and oxygen with the formula Ho2O3. Together with dysprosium(III) oxide (Dy2O3), holmium oxide is one of the most powerfully paramagnetic substances known. The oxide, also called holmia, occurs as a component of the related erbium oxide mineral called erbia. Typically, the oxides of the trivalent lanthanides coexist in nature, and separation of these components requires specialized methods. Holmium oxide is used in making specialty colored glasses. Glass containing holmium oxide and holmium oxide solutions have a series of sharp optical absorption peaks in the visible spectral range. They are therefore traditionally used as a convenient calibration standard for optical spectrophotometers.
Carl Axel Arrhenius was an officer in the Swedish army as well as an amateur geologist and chemist. He is best known for his discovery of the mineral ytterbite in 1787.
Yttrium is a chemical element with the symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost always found in combination with lanthanide elements in rare-earth minerals, and is never found in nature as a free element. 89Y is the only stable isotope, and the only isotope found in the Earth's crust.
A dopant, also called a doping agent, is a trace of impurity element that is introduced into a chemical material to alter its original electrical or optical properties. The amount of dopant necessary to cause changes is typically very low. When doped into crystalline substances, the dopant's atoms get incorporated into its crystal lattice. The crystalline materials are frequently either crystals of a semiconductor such as silicon and germanium for use in solid-state electronics, or transparent crystals for use in the production of various laser types; however, in some cases of the latter, noncrystalline substances such as glass can also be doped with impurities.
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