Crystal bar process
Encyclopedia
The crystal bar process (also known as iodide process or the van Arkel–de Boer process) was developed by Anton Eduard van Arkel
and Jan Hendrik de Boer
in 1925. This process was the first industrial process for the commercial production of pure ductile metallic zirconium
. It is used in the production of small quantities of ultra-pure 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 This process was superseded commercially by the Kroll process
.
, zirconium
, hafnium
, vanadium
, thorium
or protactinium
is heated in an evacuated vessel with a halogen 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 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, zirconium and hafnium, and in fact is still in use today on a much smaller scale for special purity needs.
Anton Eduard van Arkel
Anton Eduard van Arkel, was a Dutch chemist.-See also:*Crystal bar process*Hafnium*Jan Hendrik de Boer*Titanium*Van Arkel-Ketelaar triangle-References:...
and Jan Hendrik de Boer
Jan Hendrik de Boer
Jan Hendrik de Boer was a Dutch physicist and chemist.De Boer was born in Ruinen, now De Wolden, and died in 's-Gravenzande...
in 1925. This process was the first industrial process for the commercial production of pure ductile metallic zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...
. It is used in the production of small quantities of ultra-pure 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
Kroll process
Kroll Process is a pyrometallurgical industrial process used to produce metallic titanium. It was invented by William J. Kroll in Luxembourg. After moving to the United States, Kroll further developed the method for the production of zirconium...
.
Process
As seen in the diagram below, impure titaniumTitanium
Titanium is a chemical element with the symbol Ti and atomic number 22. It has a low density and is a strong, lustrous, corrosion-resistant transition metal with a silver color....
, zirconium
Zirconium
Zirconium is a chemical element with the symbol Zr and atomic number 40. The name of zirconium is taken from the mineral zircon. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium...
, hafnium
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 zirconium minerals. Its existence was predicted by Dmitri Mendeleev in 1869. Hafnium was the penultimate stable...
, vanadium
Vanadium
Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery gray, ductile and malleable transition metal. The formation of an oxide layer stabilizes the metal against oxidation. The element is found only in chemically combined form in nature...
, thorium
Thorium
Thorium is a natural radioactive chemical element with the symbol Th and atomic number 90. It was discovered in 1828 and named after Thor, the Norse god of thunder....
or protactinium
Protactinium
Protactinium is a chemical element with the symbol Pa and atomic number 91. It is a dense, silvery-gray metal which readily reacts with oxygen, water vapor and inorganic acids. It forms various chemical compounds where protactinium is usually present in the oxidation state +5, but can also assume...
is heated in an evacuated vessel with a halogen at 50–250 °C. The patent specifically involved the intermediacy of TiI4
Titanium tetraiodide
Titanium tetraiodide is an inorganic compound with the formula TiI4. It is a rare molecular binary metal iodide, consisting of isolated molecules of tetrahedral Ti centers. Reflecting its molecular character, TiI4 can be distilled without decomposition at one atmosphere; this property is the...
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 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, zirconium and hafnium, and in fact is still in use today on a much smaller scale for special purity needs.