Van Arkel–de Boer Process
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Van Arkel–de Boer Process
The van Arkel–de Boer process, also known as the iodide process or crystal-bar process, was the first industrial process for the commercial production of pure ductile titanium, zirconium and some other metals. It was developed by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925. Now it is used in the production of small quantities of ultrapure titanium and zirconium. It primarily involves the formation of the metal iodides and their subsequent decomposition to yield pure metal. This process was superseded commercially by the Kroll process. Process As seen in the diagram below, impure titanium, zirconium, hafnium, vanadium, thorium or protactinium Protactinium (formerly protoactinium) is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds ... is heated in an evacuated vessel with a halogen at 50–250 °C. The ...
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Titanium
Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in sea water, aqua regia, and chlorine. Titanium was discovered in Cornwall, Great Britain, by William Gregor in 1791 and was named by Martin Heinrich Klaproth after the Titans of Greek mythology. The element occurs within a number of minerals, principally rutile and ilmenite, which are widely distributed in the Earth's crust and lithosphere; it is found in almost all living things, as well as bodies of water, rocks, and soils. The metal is extracted from its principal mineral ores by the Kroll and Hunter processes. The most common compound, titanium dioxide, is a popular photocatalyst and is used in the manufacture of white pigments. Other compounds include titanium tetrachloride (TiCl4), a component of smoke screens and catalysts; and ...
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Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name ''zirconium'' is taken from the name of the mineral zircon, the most important source of zirconium. The word is related to Persian '' zargun'' (zircon; ''zar-gun'', "gold-like" or "as gold"). It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, four of which are stable. Zirconium compounds have no known biological role. Characteristics Zirconium is a lustrous, greyish-white, soft, ductile, malleable metal that is solid at room temperature, though it is hard and brittle at lesser purities. In powder form, zirconium is highl ...
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Anton Eduard Van Arkel
Anton Eduard van Arkel, (19 November 1893 – 14 March 1976) was a Dutch chemist. Van Arkel suggested the names "pnictogen" and "pnictide" to refer to chemical elements in group 15 (the nitrogen group or nitrogen family) of the periodic table. Van Arkel, together with Jan Hendrik de Boer, developed a method for the preparation of very pure tungsten: the dissociation of the vapor of tungsten chloride on an incandescent core wire known as the Van Arkel–de Boer process. This method was later used by himself and others for many other metals and non-metals. Van Arkel and de Boer thus provided the first method to fabricate pure titanium. Van Arkel became member of the Royal Netherlands Academy of Arts and Sciences in 1962. See also *Crystal bar process *Hafnium *Jan Hendrik de Boer *Titanium *Van Arkel–Ketelaar triangle Bond triangles or Van Arkel–Ketelaar triangles (named after Anton Eduard van Arkel and J. A. A. Ketelaar) are triangles used for showing different compo ...
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Jan Hendrik De Boer
Jan Hendrik de Boer (19 March 1899 – 25 April 1971) was a Dutch physicist and chemist. De Boer was born in Ruinen, De Wolden, and died in The Hague. He studied at the University of Groningen and was later employed in industry. Together with Anton Eduard van Arkel, de Boer developed a chemical transport reaction for titanium, zirconium, and hafnium known as the crystal bar process. In a closed vessel the metal reacts with iodine at elevated temperature forming the iodide. At a tungsten filament of 1700 °C the reverse reaction occurs, and the iodine and the metal are set free. The metal forms a solid coating at the tungsten filament and the iodine can react with additional metal, resulting in a steady turnover. ::M + 2I2 (>400 °C) → MI4 ::MI4 (1700 °C) → M + 2I2 De Boer became a member of the Royal Netherlands Academy of Arts and Sciences in 1940, and foreign member in 1947. See also *Metal–insulator transition *Van Arkel–de Boer process The va ...
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Kroll Process
The Kroll process is a pyrometallurgical industrial process used to produce metallic titanium from titanium tetrachloride. The Kroll process replaced the Hunter process for almost all commercial production. Process In the Kroll process, the TiCl4 is reduced by liquid magnesium to give titanium metal: :TiCl4 + 2Mg -> 25^oCi + 2MgCl2 The reduction is conducted at 800–850 °C in a stainless steel retort. Complications result from partial reduction of the TiCl4, giving to the lower chlorides TiCl2 and TiCl3. The MgCl2 can be further refined back to magnesium. The resulting porous metallic titanium sponge is purified by leaching or vacuum distillation. The sponge is crushed, and pressed before it is melted in a consumable carbon electrode vacuum arc furnace. The melted ingot is allowed to solidify under vacuum. It is often remelted to remove inclusions and ensure uniformity. These melting steps add to the cost of the product. Titanium is about six times as expensive as ...
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Hafnium
Hafnium is a chemical element with the symbol Hf and atomic number 72. A lustrous, silvery gray, tetravalent transition metal, hafnium chemically resembles zirconium and is found in many zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869, though it was not identified until 1923, by Dirk Coster and George de Hevesy, making it the penultimate stable element to be discovered (the last being rhenium in 1925). Hafnium is named after , the Latin name for Copenhagen, where it was discovered. Hafnium is used in filaments and electrodes. Some semiconductor fabrication processes use its oxide for integrated circuits at 45 nanometers and smaller feature lengths. Some superalloys used for special applications contain hafnium in combination with niobium, titanium, or tungsten. Hafnium's large neutron capture cross section makes it a good material for neutron absorption in control rods in nuclear power plants, but at the same time requires that it be removed from th ...
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Vanadium
Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer ( passivation) somewhat stabilizes the free metal against further oxidation. Spanish scientist Andrés Manuel del Río discovered compounds of vanadium in 1801 in Mexico by analyzing a new lead-bearing mineral he called "brown lead". Though he initially presumed its qualities were due to the presence of a new element, he was later erroneously convinced by French chemist Hippolyte Victor Collet-Descotils that the element was just chromium. Then in 1830, Nils Gabriel Sefström generated chlorides of vanadium, thus proving there was a new element, and named it "vanadium" after the Scandinavian goddess of beauty and fertility, Vanadís (Freyja). The name was based on the wide range of colors found in vanadium compounds. Del Rio's lead mineral was ...
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Thorium
Thorium is a weakly radioactive metallic chemical element with the symbol Th and atomic number 90. Thorium is silvery and tarnishes black when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high melting point. Thorium is an electropositive actinide whose chemistry is dominated by the +4 oxidation state; it is quite reactive and can ignite in air when finely divided. All known thorium isotopes are unstable. The most stable isotope, 232Th, has a half-life of 14.05 billion years, or about the age of the universe; it decays very slowly via alpha decay, starting a decay chain named the thorium series that ends at stable 208 Pb. On Earth, thorium and uranium are the only significantly radioactive elements that still occur naturally in large quantities as primordial elements. Thorium is estimated to be over three times as abundant as uranium in the Earth's crust, and is chiefly refined from monazite sands as a by-product of extracti ...
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Protactinium
Protactinium (formerly protoactinium) is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray actinide metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds in which protactinium is usually present in the oxidation state +5, but it can also assume +4 and even +3 or +2 states. Concentrations of protactinium in the Earth's crust are typically a few parts per trillion, but may reach up to a few parts per million in some uraninite ore deposits. Because of its scarcity, high radioactivity and high toxicity, there are currently no uses for protactinium outside scientific research, and for this purpose, protactinium is mostly extracted from spent nuclear fuel. The element was first identified in 1913 by Kazimierz Fajans and Oswald Helmuth Göhring and named ''brevium'' because of the short half-life of the specific isotope studied, i.e. protactinium-234. A more stable isotope of protactinium, 231Pa, ...
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Titanium Tetraiodide
Titanium tetraiodide is an inorganic compound with the formula TiI4. It is a black volatile solid, first reported by Rudolph Weber in 1863. It is an intermediate in the van Arkel–de Boer process for the purification of titanium. Physical properties TiI4 is a rare molecular binary metal iodide, consisting of isolated molecules of tetrahedral Ti(IV) centers. The Ti-I distances are 261 pm. Reflecting its molecular character, TiI4 can be distilled without decomposition at one atmosphere; this property is the basis of its use in the van Arkel–de Boer process. The difference in melting point between TiCl4 (m.p. -24 °C) and TiI4 (m.p. 150 °C) is comparable to the difference between the melting points of CCl4 (m.p. -23 °C) and CI4 (m.p. 168 °C), reflecting the stronger intermolecular van der Waals bonding in the iodides. Two polymorphs of TiI4 exist, one of which is highly soluble in organic solvents. In the less soluble cubic form, the Ti-I distances are 261 ...
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Zirconium Tetraiodide
Zirconium(IV) iodide is the chemical compound with the formula Zr I4. It is the most readily available iodide of zirconium. It is an orange-coloured solid that degrades in the presence of water. The compound was once prominent as an intermediate in the purification of zirconium metal. Structure Like most binary metal halides, zirconium(IV) iodide adopts a polymeric structure. As characterized by X-ray crystallography, the compound consists of octahedral Zr(IV) centers interconnected by four doubly bridging iodide ligands. The Zr-I distances of 2.692 (terminal) and 3.030 Å Synthesis and reactions This compound is volatile, subliming as intact tetrahedral ZrI4 molecules. It is prepared by the direct reaction of powdered zirconium metal and iodine.. Pyrolysis of zirconium(IV) iodide gas by contact of hot wire was the first industrial process for the commercial production of pure ductile metallic zirconium. This crystal bar process was developed by Anton Eduard van Arkel and Jan ...
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