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rhenium

 
Dictionary: rhe·ni·um   (rē'nē-əm) pronunciation
 
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n. (Symbol Re)

A rare, dense, silvery-white metallic element with a very high melting point used for electrical contacts and with tungsten for high-temperature thermocouples. Atomic number 75; atomic weight 186.2; melting point 3,180°C; boiling point 5,627°C; specific gravity 21.02; valence 1, 2, 3, 4, 5, 6, 7.

[From Latin Rhēnus, the Rhine.]


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Sci-Tech Encyclopedia: Rhenium
 
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A chemical element, Re, with atomic number 75 and atomic weight 186.2. Rhenium is a transition element. It is a dense metal (21.04) with the very high melting point of 3440°C (6220°F). See also Periodic table.

Rhenium is similar to its homolog technetium in that it may be oxidized at elevated temperatures by oxygen to form the volatile heptoxide, Re2O7; this in turn may be reduced to a lower oxide, ReO2. The compounds ReO3, Re2O3, and Re2O, are well known. Perrhenic acid, HReO4, is a strong monobasic acid and is only a very weak oxidizing agent. Complex perrhenates, such as cobalt hexammine perrhenate, [Co(NH3)6(ReO4)3], are also known.

The halogen compounds of rhenium are very complicated, and a large series of halides and oxyhalides have been reported. Rhenium forms two well-characterized sulfides, Re2S7 and ReS2, as well as two selenides, Re2Se7 and ReSe2. The sulfides have their counterparts in the technetium compounds, Tc2S7 and TcS2. See also Transition elements.

 
Columbia Encyclopedia: rhenium
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rhenium (rē'nēəm) , metallic chemical element; symbol Re; at. no. 75; at. wt. 186.207; m.p. about 3,180°C; b.p. about 5,625°C; sp. gr. 21.02 at 20°C; valence −1, +2, +3, +4, +5, +6, or +7. Rhenium is a very dense, high-melting, silver-white metal. Of the elements, only carbon and tungsten have higher melting points and only iridium, osmium, and platinum are more dense. The chemical properties of rhenium are like those of technetium, the element above it in Group 7 of the periodic table. A number of rhenium compounds are known, among them halides, oxides, and sulfides. The heptavalent oxide, Re2O7, on dissolving in water forms perrhenic acid, HReO4, from which many other compounds are prepared. Rhenium is not found uncombined in nature. It is widely distributed in the earth's crust in platinum and molybdenum ores and in many minerals, but is not abundant. In the United States rhenium is obtained commercially as a byproduct of the roasting of copper sulfide ores from Arizona and Utah. Rhenium metal is obtained as a powder by reduction of its compounds with hydrogen. The powder is compacted, sintered, annealed, and formed into wire, foil, rods, or strips. Rhenium is used in alloys with tungsten; it gives improved ductility and high-temperature strength. These alloys are used for electrical contacts, electronic filaments, and thermocouples and in photographic flash lamps. Rhenium forms a superconductive alloy with molybdenum. Rhenium is used as a catalyst for hydrogenation and petroleum cracking. Based on his periodic law, Mendeleev predicted the existence of rhenium, which he called dvi-manganese. The accuracy of prediction of the properties of the element led to its discovery in 1925 by Walter Nodack, Ida Tacke, and Otto Berg in platinum ores and the mineral columbite.

 
Veterinary Dictionary: rhenium
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A chemical element, atomic number 75, atomic weight 186.2, symbol Re.

 
Wikipedia: Rhenium
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75 tungsten ← rhenium → osmium
Tc
↑
Re
↓
Bh
General
Name, Symbol, Number rhenium, Re, 75
Element category transition metals
Group, Period, Block 7, 6, d
Appearance grayish white
Standard atomic weight 186.207(1)  g·mol−1
Electron configuration [Xe] 4f14 5d5 6s2
Electrons per shell 2, 8, 18, 32, 13, 2
Physical properties
Phase solid
Density (near r.t.) 21.02  g·cm−3
Liquid density at m.p. 18.9  g·cm−3
Melting point 3459 K
(3186 °C, 5767 °F)
Boiling point 5869 K
(5596 °C, 10105 °F)
Heat of fusion 60.43  kJ·mol−1
Heat of vaporization 704  kJ·mol−1
Specific heat capacity (25 °C) 25.48  J·mol−1·K−1
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
at T(K) 3303 3614 4009 4500 5127 5954
Atomic properties
Crystal structure hexagonal
Oxidation states 7, 6, 5, 4, 3, 2, 1, 0, -1
(mildly acidic oxide)
Electronegativity 1.9 (Pauling scale)
Ionization energies
(more)		 1st: 760 kJ·mol−1
2nd: 1260 kJ·mol−1
3rd: 2510  kJ·mol−1
Atomic radius 137  pm
Covalent radius 151±7  pm
Miscellaneous
Magnetic ordering paramagnetic[1]
Electrical resistivity (20 °C) 193 n Ω·m
Thermal conductivity (300 K) 48.0  W·m−1·K−1
Thermal expansion (25 °C) 6.2  µm·m−1·K−1
Speed of sound (thin rod) (20 °C) 4700 m/s
Young's modulus 463  GPa
Shear modulus 178  GPa
Bulk modulus 370  GPa
Poisson ratio 0.30
Mohs hardness 7.0
Vickers hardness 2450  MPa
Brinell hardness 1320  MPa
CAS registry number 7440-15-5
Most-stable isotopes
Main article: Isotopes of rhenium
iso NA half-life DM DE (MeV) DP
185Re 37.4% 185Re is stable with 110 neutrons
187Re 62.6% 4.35×1010 y α (not observed) 1.653 183Ta
β- 0.0026 187Os
References

Rhenium (pronounced /ˈriːniəm/) is a chemical element with the symbol Re and atomic number 75. It is a silvery-white, heavy, third-row transition metal in group 7 of the periodic table. With an average concentration of 1 part per billion (ppb), rhenium is one of the rarest elements in the Earth's crust. Rhenium resembles manganese chemically and is obtained as a by-product of molybdenum and copper refinement. Rhenium shows in its compounds a wide variety of oxidation states ranging from −1 to +7.

Minor amounts of rhenium are added into tungsten alloys and some rhenium compounds are used as catalysts in the chemical industry. Nickel-based superalloys for the use in jet engines contain up to 6% of rhenium, making it the largest use for rhenium. Because of the low availability and the demand for jet engines, rhenium is among the most expensive metals on Earth, whose price at times exceeds US$12,000 per kilogram. Rhenium, discovered in 1925, was the last naturally occurring stable element to be discovered. Francium was the last identified naturally-occurring element, but it is unstable. Rhenium was named after the river Rhine.

Contents

History

Rhenium (Latin Rhenus meaning Rhine)[2] was the next-to-last naturally occurring element to be discovered and the last element to be discovered having a stable isotope.[3] The existence of a yet undiscovered element at this position in the periodic table had been predicted by Henry Moseley in 1914.[4] It is generally considered to have been discovered by Walter Noddack, Ida Tacke, and Otto Berg in Germany. In 1925 they reported that they detected the element in platinum ore and in the mineral columbite. They also found rhenium in gadolinite and molybdenite.[5] In 1928 they were able to extract 1 g of the element by processing 660 kg of molybdenite.[6] The process was so complicated and expensive that production was discontinued until early 1950 when tungsten-rhenium and molybdenum-rhenium alloys were prepared. These alloys found important applications in industry that resulted in a great demand for the rhenium produced from the molybdenite fraction of porphyry copper ores.

In 1908, Japanese chemist Masataka Ogawa announced that he discovered the 43rd element and named it nipponium (Np) after Japan (which is Nippon in Japanese). However, later analysis indicated the presence of rhenium (element 75), not element 43.[7] The symbol Np was later used for the element neptunium.

Characteristics

Rhenium is a silvery-white metal with one of the highest melting points of all elements, exceeded by only tungsten and carbon. It is also one of the densest, exceeded only by platinum, iridium and osmium.

Its usual commercial form is a powder, but this element can be consolidated by pressing and sintering in a vacuum or hydrogen atmosphere. This procedure yields a compact having the density above 90% of the density of the metal. When annealed this metal is very ductile and can be bent, coiled, or rolled.[8] Rhenium-molybdenum alloys are superconductive at 10 K; tungsten-rhenium alloys are also superconductive[9] around 4-8 K, depending on the alloy. Rhenium metal superconducts at 2.4 K.[10][11]

Isotopes

Main article: Isotopes of rhenium

Naturally occurring rhenium is 37.4% 185Re, which is stable, and 62.6% 187Re, which is unstable but has a very long half-life (~1010 years); that lifetime is affected by the charge state of rhenium atom[12][13]. The beta decay of 187Re is used for rhenium-osmium dating of ores. The available energy for this beta decay (2.6 keV) is one of the lowest known among all radionuclides. There are twenty-six other recognized radioactive isotopes of rhenium.[14]

Compounds

See also: Category:Rhenium compounds

Rhenium has the widest range of oxidation states of any known element: −1, 0, +1, +2, +3, +4, +5, +6 and +7.[15] The oxidation states +7, +6, +4, and +2 are the most common.[15]

The most common rhenium compounds are the oxides and the halides exhibiting a broad oxidation number spectrum: Re2O7, ReO3, Re2O5, ReO2, and Re2O3 are the known oxides, and ReF7, ReCl6, ReCl5, ReCl4 and ReCl3 are a few of the known halogen derivatives.[16] Known sulfides are ReS2 and Re2S7.[16]

Rhenium is most available commercially as the sodium and ammonium perrhenates. It is also readily available as dirhenium decacarbonyl; these three compounds are common entry points to rhenium chemistry. Various perrhenate salts may be easily converted to tetrathioperrhenate by the action of ammonium hydrosulfide.[17] It is possible to reduce the dirhenium decacarbonyl Re2(CO)10 by reacting it with sodium amalgam to Na[Re(CO)5] with rhenium in the formal oxidation state -1.[18] Dirhenium decacarbonyl may be oxidatively cleaved with bromine to give bromopentacarbonylrhenium(I),[19] then reduced with zinc and acetic acid to pentacarbonylhydridorhenium:[20]

Re2(CO)10 + Br2 → Re(CO)5Br
Re(CO)5Br + Zn + HOAc → Re(CO)5H + ZnBr(OAc)

Bromopentacarbonylrhenium(I) may be decarbonylated to give the rhenium tricarbonyl fragment either by refluxing in water:[21]

Re(CO)5Br + 3 H2O → [Re(CO)3(H2O)3]Br + 2 CO

or by reacting with tetraethylammonium bromide:[22]

Re(CO)5Br + 2 (NEt4Br → [NEt4]2[Re(CO)3Br3]

Rhenium diboride (ReB2) is a hard compound having the hardness similar to that of tungsten carbide, silicon carbide, titanium diboride or zirconium diboride.[23]

Rhenium was originally thought to form the rhenide anion, Re−, in which it has the −1 oxidation state. This was based on the product of the reduction of perrhenate salts, such as the reduction of potassium perrhenate (KReO4) by potassium metal.[24] "Potassium rhenide" was shown to exist as a tetrahydrated complex, with the postulated chemical formula KRe·4H2O.[25] This compound exhibits strongly reducing properties, and slowly yields hydrogen gas when dissolved in water. The lithium and thallous salts were also reported. Later research, however, indicates that the "rhenide" ion is actually a hydridorhenate complex. "Potassium rhenide" was shown to be in fact the nonahydridorhenate, K2ReH9, containing the ReH2−9 anion in which the oxidation state of rhenium is actually +7.[26][27] Other methods of reduction of perrhenate salts yield compounds containing other hydrido- complexes, including ReH3(OH)3(H2O)−.[28]

Occurrence

Molybdenite

Rhenium is one of the rarest elements in Earth's crust with a average concentration of 1 ppb;[16] other sources quote the number of 0.5 ppb making it the 77th most abundant element in Earth's crust.[29] Rhenium is probably not found free in nature (its possible natural occurrence is uncertain), but occurs in amounts up to 0.2%[16] in the mineral molybdenite, the major commercial source, although single molybdenite samples with up to 1.88% have been found.[30] Chile has the world's largest rhenium reserves, part of the copper ore deposits, and was the leading producer as of 2005.[31] It was only recently that the first rhenium mineral was found and described (in 1994), a rhenium sulfide mineral (ReS2) condensing from a fumarole on Russia's Kudriavy volcano, in the Kurile Islands.[32] Named rheniite, this rare mineral commands high prices among collectors,[33] but is not an economically viable source of the element.

Production

Ammonium perrhenate

Commercial rhenium is extracted from molybdenum roaster-flue gas obtained from copper-sulfide ores. Some molybdenum ores contain 0.001% to 0.2% rhenium.[16][30] Rhenium(VII) oxide and perrhenic acid readily dissolve in water; they are leached from flue dusts and gasses and extracted by precipitating with potassium or ammonium chloride as the perrhenate salts, and purified by recrystallization.[34] Total world production is between 40 and 50 tons/year; the main producers are in Chile, the United States, and Kazakhstan.[35] Recycling of used Pt-Re catalyst and special alloys allow the recovery of another 10 tons per year. Prices for the metal rose rapidly in early 2008, from $1000–$2000 per kg in 2003-2006 to over $10,000 in February 2008.[36][37] The metal form is prepared by reducing ammonium perrhenate with hydrogen at high temperatures:[34]

2 NH4ReO4 + 7 H2 → 2 Re + 8 H2O + 2 NH3

Applications

The F-15 engine uses rhenium containing second-generation superalloys

Rhenium is added to high-temperature superalloys that are used to make jet engine parts, making 70% of the worldwide rhenium production.[38] Another major application is in platinum-rhenium catalysts, which are primarily used in making lead-free, high-octane gasoline.[35][39]

Alloys

The nickel-based superalloys have improved creep strength with the addition of rhenium. The alloys normally contain 3% or 6% of rhenium.[40] The second generation alloys contain 3%; these alloys were used in the engines of the F-16 and F-15, while the new single-crystal third-generation alloys contain 6% of rhenium; they are used in the F-22 and F-35 engines.[39][41] For 2006 the consumption is given as 28% for General Electric, 28% Rolls-Royce plc and 12% Pratt & Whitney, all for superalloys, while the use for catalysts only accounts for 14% and the remaining applications use 18%.[38] In 2006, 77% of the rhenium consumption in the United States was in alloys.[39]

Rhenium improves the properties of tungsten and is therefore the most important alloying material for tungsten. Tungsten-rhenium alloys are more ductile at low temperature making them easier to machine, while the high-temperature stability is also improved. The effect increases with the rhenium concentration, and therefore tungsten alloys are produced with up to 27% of Re, which is the solubility limit.[42] One application for the tungsten-rhenium alloys is x-ray sources. The high melting point of both compounds, together with the high atomic mass, makes them stable against the prolonged electron impact.[43] Rhenium tungsten alloys are also applied as thermocouples to measure temperatures up to 2200 °C.[44]

The high temperature stability, low vapor pressure, good wear resistance and ability to withstand arc corrosion of rhenium are useful in self-cleaning electrical contacts. In particular, the discharge occurring during the switching oxidizes the contacts. However, rhenium oxide Re2O7 has poor stability (sublimates at ~360 °C) and therefore is removed during the discharge.[38]

Rhenium has a high melting point and a low vapor pressure similar to tantalum and tungsten, however, rhenium forms no volatile oxides. Therefore, rhenium filaments exhibit a higher stability if the filament is operated not in vacuum, but in oxygen-containing atmosphere.[45] Those filaments are widely used in mass spectrographs, in ion gauges.[46] and in photoflash lamps in photography.[47]

Catalysts

Rhenium in the form of rhenium-platinum alloy is used as catalyst for catalytic reforming, which is a chemical process to convert petroleum refinery naphthas with low octane ratings into high-octane liquid products. Worldwide, 30% of catalysts used for this process contain rhenium.[48] The olefin metathesis is the other reaction for which rhenium is used as catalyst. Normally Re2O7 on alumina is used for this process.[49] Rhenium catalysts are very resistant to chemical poisoning from nitrogen, sulfur and phosphorus, and so are used in certain kinds of hydrogenation reactions.[8][50][51]

Other uses

188Rh and 186Rh isotopes are radioactive and are used for treatment of liver cancer. They both have similar penetration depth in tissue (5 mm for 186Rh and 11 mm for 188Rh), but 186Re has advantage of longer lifetime (90 hours vs. 17 hours).[52][53]

Related by periodic trends, rhenium has a similar chemistry with technetium; work done to label rhenium onto target compounds can often be translated to technetium. This is useful for radiopharmacy, where it is difficult to work with technetium - especially the 99m isotope used in medicine - due to its expense and short half-life.[52][54]

Precaution

Very little is known about the toxicity of rhenium and its compounds because they are used in very small amounts. Soluble salts, such as the rhenium halides or perrhenates, could be hazardous due to elements other than rhenium or due to rhenium itself.[55] Only a few compounds of rhenium have been tested for their toxicity; two examples are potassium perrhenate and rhenium trichloride, which were injected as a solution into rats. The perrhenate had an LD50 value of 2800 mg/kg after seven days and the rhenium trichloride showed LD50 of 280 mg/kg.[56]

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