Van Arkel–de Boer Process
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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 Titanium is a chemical element; it has 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 ...
,
zirconium Zirconium is a chemical element; it has Symbol (chemistry), symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyis ...
and some other metals. It was developed by
Anton Eduard van Arkel Anton Eduard van Arkel, (19 November 1893 – 14 March 1976) was a Dutch chemist. Biography In the early 1920s Van Arkel, together with Jan Hendrik de Boer, working for Philips NV, developed the Van Arkel–de Boer process for the preparati ...
and
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 wi ...
in 1925 for
Philips Nv Koninklijke Philips N.V. (), simply branded Philips, is a Dutch multinational health technology company that was founded in Eindhoven in 1891. Since 1997, its world headquarters have been situated in Amsterdam, though the Benelux headquarter ...
. Now, it is used in the production of small quantities of ultrapure titanium and zirconium. It primarily involves the formation of the metal
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
s and their subsequent decomposition to yield pure metal, for example, at one of the
Allegheny Technologies ATI Inc. (previously Allegheny Technologies Incorporated) is an American producer of specialty materials headquartered in Dallas, Texas. ATI produces metals including titanium and titanium alloys, nickel-based alloys and superalloys, stainles ...
' Albany plants. This process was superseded commercially by the
Kroll process The Kroll process is a pyrometallurgical industrial process used to produce metallic titanium from titanium tetrachloride. As of 2001 William Justin Kroll's process replaced the Hunter process for almost all commercial production. Process In the ...
(based on the reduction of
titanium tetrachloride Titanium tetrachloride is the inorganic compound with the formula . It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. is a volatile liquid. Upon contact with humid air, it forms thick clouds o ...
by metallic
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
).


Process

As seen in the diagram, impure titanium, zirconium,
hafnium Hafnium is a chemical element; it has 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 Dm ...
,
vanadium Vanadium is a chemical element; it has Symbol (chemistry), 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 ...
,
thorium Thorium is a chemical element; it has symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive grey when it is exposed to air, forming thorium dioxide; it is moderately soft, malleable, and ha ...
or
protactinium Protactinium is a chemical element; it has symbol Pa and atomic number 91. It is a dense, radioactive, silvery-gray actinide metal which readily reacts with oxygen, water vapor, and inorganic acids. It forms various chemical compounds, in which p ...
is heated in an evacuated vessel with a
halogen The halogens () are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would ...
at 50–250 °C. The patent specifically involved the intermediacy of TiI4 and ZrI4, which were volatilized (leaving impurities as solid). At atmospheric pressure TiI4 melts at 150 °C and boils at 377 °C, while ZrI4 melts at 499 °C and boils at 600 °C. The boiling points are lower at reduced pressure. The gaseous metal tetraiodide is decomposed on a white hot
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
filament (1400 °C). As more metal is deposited the filament conducts better and thus a greater electric current is required to maintain the temperature of the filament. The process can be performed in the span of several hours or several weeks, depending on the particular setup. Generally, the crystal bar process can be performed using any number of metals using whichever halogen or combination of halogens is most appropriate for that sort of transport mechanism, based on the reactivities involved. The only metals it has been used to purify on an industrial scale are
titanium Titanium is a chemical element; it has 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 ...
,
zirconium Zirconium is a chemical element; it has Symbol (chemistry), symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyis ...
and
hafnium Hafnium is a chemical element; it has 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 Dm ...
, and in fact it is still in use today on a much smaller scale for special purity needs.


References

Industrial processes Zirconium Dutch inventions Methods of crystal growth Titanium processes Metallurgical processes Materials science 1925 introductions 20th-century inventions {{industry-stub