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Tungsten

Chemical element with atomic number 74 (W)

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The free element is remarkable for its robustness, especially the fact that it has the highest melting point of all known elements, at 3,422 °C (6,192 °F; 3,695 K). It also has the highest boiling point, at 5,930 °C (10,706 °F; 6,203 K). Its density is 19.254 g/cm3, comparable with that of uranium and gold, and much higher (about 1.7 times) than that of lead. Polycrystalline tungsten is an intrinsically brittle and hard material (under standard conditions, when uncombined), making it difficult to work into metal. However, pure single-crystalline tungsten is more ductile and can be cut with a hard-steel hacksaw.

Tungsten occurs in many alloys, which have numerous applications, including incandescent light bulb filaments, X-ray tubes, electrodes in gas tungsten arc welding, superalloys, and radiation shielding. Tungsten's hardness and high density make it suitable for military applications in penetrating projectiles. Tungsten compounds are often used as industrial catalysts. Its largest use is in tungsten carbide, a wear-resistant material used in metalworking, mining, and construction. About 50% of tungsten is used in tungsten carbide, with the remaining major use being alloys and steels: less than 10% is used in other compounds.

Tungsten is the only metal in the third transition series that is known to occur in biomolecules, found in a few species of bacteria and archaea. However, tungsten interferes with molybdenum and copper metabolism and is somewhat toxic to most forms of animal life.

Characteristics

Physical properties

In its raw form, tungsten is a hard steel-grey metal that is often brittle and hard to work. Purified, monocrystalline tungsten retains its hardness (which exceeds that of many steels), and becomes malleable enough that it can be worked easily. It can be worked by forging, drawing, rolling, or extruding. Most materials based on tungsten are formed by sintering tungsten powder along with additives, though this results in a more porous final product.

Of all metals in pure form, tungsten has the highest melting point (3,422 °C, 6,192 °F), lowest vapor pressure (at temperatures above 1,650 °C, 3,000 °F), and the highest tensile strength. Although carbon remains solid at higher temperatures than tungsten, carbon sublimes at atmospheric pressure instead of melting, so it has no melting point. Moreover, tungsten's most stable crystal phase does not exhibit any high-pressure-induced structural transformations for pressures up to at least 364 gigapascals. Tungsten has the lowest coefficient of thermal expansion of any pure metal. The low thermal expansion and high melting point and tensile strength of tungsten originate from strong covalent bonds formed between tungsten atoms by the 5d electrons. Alloying small quantities of tungsten with steel greatly increases its toughness.

Tungsten exists in two major crystalline forms: α and β. The former has a body-centered cubic structure and is the more stable form. The structure of the β phase is called A15 cubic; it is metastable, but can coexist with the α phase at ambient conditions owing to non-equilibrium synthesis or stabilization by impurities. Contrary to the α phase which crystallizes in isometric grains, the β form exhibits a columnar habit. The α phase has one third of the electrical resistivity and a much lower superconducting transition temperature Tc relative to the β phase: ca. 0.015 K vs. 1–4 K; mixing the two phases allows obtaining intermediate Tc values. The Tc value can also be raised by alloying tungsten with another metal (e.g. 7.9 K for W-Tc). Such tungsten alloys are sometimes used in low-temperature superconducting circuits.

Isotopes

Naturally occurring tungsten consists of four stable isotopes (182W, 183W, 184W, and 186W) and one very long-lived radioisotope, 180W. Theoretically, all five can decay into isotopes of element 72 (hafnium) by alpha emission, but only 180W has been observed to do so, with a half-life of (1.8±0.2)×1018 years; on average, this yields about two alpha decays of 180W per gram of natural tungsten per year.

Another 34 artificial radioisotopes of tungsten have been characterized, the most stable of which are 181W with a half-life of 121.2 days, 185W with a half-life of 75.1 days, 188W with a half-life of 69.4 days, 178W with a half-life of 21.6 days, and 187W with a half-life of 23.72 h. All of the remaining radioactive isotopes have half-lives of less than 3 hours, and most of these have half-lives below 8 minutes. Tungsten also has 12 meta states, with the most stable being 179mW (t½ 6.4 minutes).

Chemical properties

Tungsten is a mostly non-reactive element: it does not react with water, is immune to attack by most acids and bases, and does not react with oxygen or air at room temperature. At elevated temperatures (i.e., when red-hot) it reacts with oxygen to form the trioxide compound tungsten(VI), WO3. It will, however, react directly with fluorine (F2) at room temperature to form tungsten(VI) fluoride (WF6), a colorless gas. At around 250 °C it will react with chlorine or bromine, and under certain hot conditions will react with iodine. Finely divided tungsten is pyrophoric.

The most common formal oxidation state of tungsten is +6, but it exhibits all oxidation states from −2 to +6. Tungsten typically combines with oxygen to form the yellow tungstic oxide, WO3, which dissolves in aqueous alkaline solutions to form tungstate ions, WO42−.

Tungsten carbides (W2C and WC) are produced by heating powdered tungsten with carbon. W2C is resistant to chemical attack, although it reacts strongly with chlorine to form tungsten hexachloride (WCl6).

In aqueous solution, tungstate gives the heteropoly acids and polyoxometalate anions under neutral and acidic conditions. As tungstate is progressively treated with acid, it first yields the soluble, metastable "paratungstate A" anion, W7O246−, which over time converts to the less soluble "paratungstate B" anion, H2W12O4210−. Further acidification produces the very soluble metatungstate anion, H2W12O46−, after which equilibrium is reached. The metatungstate ion exists as a symmetric cluster of twelve tungsten-oxygen octahedra known as the Keggin anion. Many other polyoxometalate anions exist as metastable species. The inclusion of a different atom such as phosphorus in place of the two central hydrogens in metatungstate produces a wide variety of heteropoly acids, such as phosphotungstic acid H3PW12O40.

Tungsten trioxide can form intercalation compounds with alkali metals. These are known as bronzes, and have the general formula of MxWO3-x, where M is an alkali metal; an example is sodium tungsten bronze. Tungsten trioxide is also intercalated with hydrogen ions in electrochromic devices, that is, devices that store a charge and change color.

In gaseous form, tungsten forms the diatomic species W2. These molecules feature a sextuple bond between tungsten atoms — the highest known bond order among stable atoms.

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