Hafnium

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Hafnium, 72Hf
Hf-crystal bar.jpg
Hafnium
Pronunciation /ˈhæfniəm/ ⓘ ​(HAF-nee-əm)
Appearancesteel gray
Standard atomic weight Ar°(Hf)
Hafnium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
Zr
↑
Hf
↓
Rf
lutetium ← hafnium → tantalum
Atomic number (Z)72
Group group 4
Period period 6
Block   d-block
Electron configuration [ Xe ] 4f14 5d2 6s2
Electrons per shell2, 8, 18, 32, 10, 2
Physical properties
Phase at  STP solid
Melting point 2506  K ​(2233 °C,​4051 °F)
Boiling point 4876 K​(4603 °C,​8317 °F)
Density (at 20° C)13.281 g/cm3  [3]
when liquid (at  m.p.)12 g/cm3
Heat of fusion 27.2  kJ/mol
Heat of vaporization 648 kJ/mol
Molar heat capacity 25.73 J/(mol·K)
Vapor pressure
P (Pa)1101001 k10 k100 k
at T (K)268929543277367941944876
Atomic properties
Oxidation states common: +4
−2, [4] 0, [5] +1, [6] +2, [7] +3 [7]
Electronegativity Pauling scale: 1.3
Ionization energies
  • 1st: 658.5 kJ/mol
  • 2nd: 1440 kJ/mol
  • 3rd: 2250 kJ/mol
Atomic radius empirical:159  pm
Covalent radius 175±10 pm
72 (Hf I) NIST ASD emission spectrum.png
Spectral lines of hafnium
Other properties
Natural occurrence primordial
Crystal structure ​ hexagonal close-packed (hcp)(hP2)
Lattice constants
Hexagonal close packed.svg
a = 319.42 pm
c = 505.12 pm (at 20 °C) [3]
Thermal expansion 5.9 µm/(m⋅K)(at 25 °C)
Thermal conductivity 23.0 W/(m⋅K)
Electrical resistivity 331 nΩ⋅m(at 20 °C)
Magnetic ordering paramagnetic [8]
Molar magnetic susceptibility +75.0×10−6 cm3/mol(at 298 K) [9]
Young's modulus 78 GPa
Shear modulus 30 GPa
Bulk modulus 110 GPa
Speed of sound thin rod3010 m/s(at 20 °C)
Poisson ratio 0.37
Mohs hardness 5.5
Vickers hardness 1520–2060 MPa
Brinell hardness 1450–2100 MPa
CAS Number 7440-58-6
History
Namingafter Hafnia . Latin for: Copenhagen, where it was discovered
Prediction Dmitri Mendeleev (1869)
Discovery and first isolation Dirk Coster and George de Hevesy (1922)
Isotopes of hafnium
Main isotopes [10] Decay
Isotope abun­dance half-life (t1/2) mode pro­duct
172Hf synth 1.87 y ε 172Lu
174Hf0.16%3.8×1016 y [11] α 170Yb
175Hfsynth69.90 d [12] ε 175Lu
176Hf5.26% stable
177Hf18.6%stable
178Hf27.3%stable
178m2Hfsynth31 y IT 178Hf
179Hf13.6%stable
180Hf35.1%stable
181Hfsynth42.39 d β− 181Ta
182Hfsynth8.90×106 yβ− 182Ta
Symbol category class.svg  Category: Hafnium
| references

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 Dmitri Mendeleev in 1869, though it was not identified until 1922 by Dirk Coster and George de Hevesy. Hafnium is named after Hafnia, the Latin name for Copenhagen, where it was discovered. The element is obtained only by separation from zirconium, with most of the world's hafnium production coming from processes that also produce zirconium. These processes make use of heavy mineral sands ore deposits, which include the minerals zircon, rutile, and ilmenite, among others.

Contents

Hafnium is most often used in alloys with nickel, and was used in larger quantities to produce the control rods used in nuclear reactors. 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 the neutron-transparent corrosion-resistant zirconium alloys used in nuclear reactors. It is ductile, and is also used in filaments and electrodes. Some semiconductor fabrication processes use its oxide for integrated circuits at 45 nanometres (1.8×10−6 in) and smaller, and superalloys used for special applications can contain hafnium in combination with niobium, titanium, or tungsten.

Pure hafnium is not toxic, but is extremely flammable to the point of being pyrophoric—capable of spontaneous combustion in air. Several industrial processes involved in the production of hafnium have by-products that can be hazardous when released into the environment, and several hafnium compounds have hazards of their own. One nuclear isomer of hafnium, 178m2Hf, was the source of a controversy for its potential use as a weapon, but it has never been successfully produced for practical use.

Characteristics

Physical characteristics

Pieces of hafnium Hafnium bits.jpg
Pieces of hafnium

Hafnium is a shiny, silvery, ductile metal [13] that is corrosion-resistant and chemically similar to zirconium [14] in that they have the same number of valence electrons and are in the same group. Also, their relativistic effects are similar: The expected expansion of atomic radii from period 5 to 6 is almost exactly canceled out by the lanthanide contraction. Hafnium changes from its alpha form, a hexagonal close-packed lattice, to its beta form, a body-centered cubic lattice, at 2,388 K (2,115 °C; 3,839 °F). [15] The physical properties of hafnium metal samples are markedly affected by zirconium impurities, especially the nuclear properties, as these two elements are among the most difficult to separate because of their chemical similarity. [14]

A notable physical difference between these metals is their density, with zirconium having about one-half the density of hafnium. The most notable nuclear properties of hafnium are its high thermal neutron capture cross section, roughly three orders of magnitude greater than that of zirconium, [13] and that the nuclei of several different hafnium isotopes readily absorb two or more neutrons apiece. [14] Because zirconium is practically transparent to thermal neutrons, it is commonly used for the metal components of nuclear reactors—especially the cladding of their nuclear fuel rods. [14]

Chemical characteristics

Hafnium dioxide (HfO2) Hafnium(IV) oxide.jpg
Hafnium dioxide (HfO2)

Hafnium reacts in air to form a protective film of hafnium oxide in the monoclinic phase that inhibits further corrosion. [16] Despite this, the metal is attacked by hydrofluoric acid and concentrated sulfuric acid, and can be oxidized with halogens [17] or burnt in air. Like its sister metal zirconium, finely divided hafnium can ignite spontaneously in air. [13] The metal is resistant to concentrated alkalis. [17]

As a consequence of lanthanide contraction, the chemistry of hafnium and zirconium is so similar that the two cannot be separated based on differing chemical reactions. The melting and boiling points of the compounds and the solubility in solvents are the major differences in the chemistry of these twin elements. [18]

Isotopes

At least 40 isotopes of hafnium have been observed, ranging in mass number from 153 to 192. [19] The five stable isotopes have mass numbers from 176 to 180 inclusive; the primordial 174Hf has a very long half-life of 3.8×1016 years. [11]

The extinct radionuclide 182Hf has a half-life of 8.90 million years, and is an important tracker isotope for the formation of planetary cores. [20] No other radioisotope has a half-life over 1.87 years. [21]

The longest-lived nuclear isomer 178m2Hf (31 years) was at the center of a controversy for several years regarding its potential use as a weapon. Because of its high energy compared to the ground state 178Hf, the isomer was put under scrutiny as being capable of induced gamma emission, which could be weaponized to produce large amounts of gamma radiation all at once. [22] Applications of the isomer have been frustrated due to the difficulty of producing it without the product being immediately destroyed [23] as well as its extremely high cost. [24]

Occurrence

Zircon crystal (2x2 cm) from Tocantins, Brazil Zircao.jpeg
Zircon crystal (2×2 cm) from Tocantins, Brazil

Hafnium is estimated to make up about between 3.0 and 4.8 ppm of the Earth's upper crust by mass. [25] : 5  [26] It does not exist as a free element on Earth, but is found combined in solid solution with zirconium in natural zirconium compounds such as zircon, ZrSiO4, which usually has about 1–4% of the Zr replaced by Hf. Rarely, the Hf/Zr ratio increases during crystallization to give the isostructural mineral hafnon (Hf,Zr)SiO4, with atomic Hf > Zr. [27] An obsolete name for a variety of zircon containing unusually high Hf content is alvite. [28]

A major source of zircon (and hence hafnium) ores is heavy mineral sands ore deposits, pegmatites, particularly in Brazil and Malawi, and carbonatite intrusions, particularly the Crown Polymetallic Deposit at Mount Weld, Western Australia. A potential source of hafnium is trachyte tuffs containing rare zircon-hafnium silicates eudialyte or armstrongite, at Dubbo in New South Wales, Australia. [29]

Production

Melted tip of a hafnium consumable electrode used in an electron beam remelting furnace, a 1 cm cube, and an oxidized hafnium electron beam-remelted ingot (left to right) Hafnium ebeam remelted.jpg
Melted tip of a hafnium consumable electrode used in an electron beam remelting furnace, a 1 cm cube, and an oxidized hafnium electron beam-remelted ingot (left to right)

The heavy mineral sands ore deposits of the titanium ores ilmenite and rutile yield most of the mined zirconium, and therefore also most of the hafnium. [30]

Zirconium is a good nuclear fuel-rod cladding metal, with the desirable properties of a very low neutron capture cross section and good chemical stability at high temperatures. However, because of hafnium's neutron-absorbing properties, hafnium impurities in zirconium would cause it to be far less useful for nuclear reactor applications. Thus, a nearly complete separation of zirconium and hafnium is necessary for their use in nuclear power. The production of hafnium-free zirconium is the main source of hafnium. [14]

Hafnium oxidized ingots which exhibit thin-film optical effects Hafnium pellets with a thin oxide layer.jpg
Hafnium oxidized ingots which exhibit thin-film optical effects

The chemical properties of hafnium and zirconium are nearly identical, which makes the two difficult to separate. [31] The methods first used—fractional crystallization of ammonium fluoride salts [32] or the fractional distillation of the chloride [33] —did not prove suitable for an industrial-scale production. After zirconium was chosen as a material for nuclear reactor programs in the 1940s, a separation method had to be developed. Liquid–liquid extraction processes with a wide variety of solvents were developed and are still used for producing hafnium. [34] Other methods to purify hafnium from zirconium include molten salt extraction and crystallization of fluorozirconates. [35] About half of all hafnium metal manufactured is produced as a by-product of zirconium refinement. The end product of the separation is hafnium(IV) chloride. [36] The purified hafnium(IV) chloride is converted to the metal by reduction with magnesium or sodium, as in the Kroll process. [37]

Further purification is effected by a chemical transport reaction developed by Arkel and de Boer: In a closed vessel, hafnium reacts with iodine at temperatures of 500 °C (900 °F), forming hafnium(IV) iodide; at a tungsten filament of 1,700 °C (3,100 °F) the reverse reaction happens preferentially, and the chemically bound iodine and hafnium dissociate into the native elements. The hafnium forms a solid coating at the tungsten filament, and the iodine can react with additional hafnium, resulting in a steady iodine turnover and ensuring the chemical equilibrium remains in favor of hafnium production. [18] [38]

Chemical compounds

Due to the lanthanide contraction, the ionic radius of hafnium(IV) (0.78 ångström) is almost the same as that of zirconium(IV) (0.79  angstroms). [39] Consequently, compounds of hafnium(IV) and zirconium(IV) have very similar chemical and physical properties. [39] Hafnium and zirconium tend to occur together in nature and the similarity of their ionic radii makes their chemical separation rather difficult. Hafnium tends to form inorganic compounds in the oxidation state of +4. Halogens react with it to form hafnium tetrahalides. [39] At higher temperatures, hafnium reacts with oxygen, nitrogen, carbon, boron, sulfur, and silicon. [39] Some hafnium compounds in lower oxidation states are known. [40]

Hafnium(IV) chloride and hafnium(IV) iodide have some applications in the production and purification of hafnium metal. They are volatile solids with polymeric structures. [18] These tetrahalides are precursors to various organohafnium compounds, [41] and hafnium(IV) chloride in particular is used in microelectronics manufacturing as a source of hafnium oxide in atomic layer deposition, much in the same way as zirconium(IV) chloride. [42]

The white hafnium oxide (HfO2), with a melting point of 2,812 °C (3,085 K; 5,094 °F) and a boiling point of roughly 5,100 °C (5,400 K; 9,200 °F), is very similar to zirconia, but slightly more basic. [18] Hafnium carbide is the most refractory binary compound known, with a melting point over 3,890 °C (4,163 K; 7,034 °F), and hafnium nitride is the most refractory of all known metal nitrides, with a melting point of 3,310 °C (3,583 K; 5,990 °F). [39] Hafnium carbonitride has the highest known melting point for any material, which is confirmed to be above 4,000 °C (4,270 K; 7,230 °F) by experiment, [43] while calculations predict its melting point to be 4,110 °C (4,380 K; 7,430 °F). [44]

History

Photographic recording of the characteristic X-ray emission lines of some elements Moseley step ladder.jpg
Photographic recording of the characteristic X-ray emission lines of some elements

Hafnium's existence was predicted by Dmitri Mendeleev in 1869. In his report on The Periodic Law of the Chemical Elements, in 1869, Dmitri Mendeleev had implicitly predicted the existence of a heavier analog of titanium and zirconium. At the time of his formulation in 1871, Mendeleev believed that the elements were ordered by their atomic masses and placed lanthanum (element 57) in the spot below zirconium. The exact placement of the elements and the location of missing elements was done by determining the specific weight of the elements and comparing the chemical and physical properties. [45]

The X-ray spectroscopy done by Henry Moseley in 1914 showed a direct dependency between spectral line and effective nuclear charge. This led to the nuclear charge, or atomic number of an element, being used to ascertain its place within the periodic table. With this method, Moseley determined the number of lanthanides and showed the gaps in the atomic number sequence at numbers 43, 61, 72, and 75. [46]

The discovery of the gaps led to an extensive search for the missing elements. In 1914, several people claimed the discovery after Henry Moseley predicted the gap in the periodic table for the then-undiscovered element 72. [47] Georges Urbain asserted that he found element 72 in the rare earth elements in 1907 and published his results on celtium in 1911. [48] Neither the spectra nor the chemical behavior he claimed matched with the element found later, and therefore his claim was turned down after a long-standing controversy. [49] The controversy was partly because the chemists favored the chemical techniques which led to the discovery of celtium, while the physicists relied on the use of the new X-ray spectroscopy method that proved that the substances discovered by Urbain did not contain element 72. [49] In 1921, Charles R. Bury [50] [51] suggested that element 72 should resemble zirconium and therefore was not part of the rare earth elements group. By early 1923, Niels Bohr and others agreed with Bury. [52] [53] These suggestions were based on Bohr's theories of the atom which were identical to chemist Charles Bury, [50] the X-ray spectroscopy of Moseley, and the chemical arguments of Friedrich Paneth. [54] [55]

Encouraged by these suggestions and by the reappearance in 1922 of Urbain's claims that element 72 was a rare earth element discovered in 1911, Dirk Coster and Georg von Hevesy were motivated to search for the new element in zirconium ores. [56] Hafnium was discovered by the two in 1923 in Copenhagen, Denmark, validating the original 1869 prediction of Mendeleev. [57] [58] [59] It was ultimately found in zircon in Norway through X-ray spectroscopy analysis. [60] The place where the discovery took place led to the element being named for the Latin name for "Copenhagen", Hafnia, the home town of Niels Bohr. [61] [62] [63] Today, the Faculty of Science of the University of Copenhagen uses in its seal a stylized image of the hafnium atom. [64]

Hafnium was separated from zirconium through repeated recrystallization of the double ammonium or potassium fluorides by Valdemar Thal Jantzen and von Hevesey. [32] Anton Eduard van Arkel and Jan Hendrik de Boer were the first to prepare metallic hafnium by passing hafnium tetraiodide vapor over a heated tungsten filament in 1924. [33] [38] This process for differential purification of zirconium and hafnium is still in use today. [14]

In 1923, six predicted elements were still missing from the periodic table: 43 (technetium), 61 (promethium), 85 (astatine), and 87 (francium) are radioactive elements and are only present in trace amounts in the environment, [65] thus making elements 75 (rhenium) and 72 (hafnium) the last two stable elements to be discovered. The element rhenium was found in 1908 by Masataka Ogawa, though its atomic number was misidentified at the time, and it was not generally recognised by the scientific community until its rediscovery by Walter Noddack, Ida Noddack, and Otto Berg in 1925. This makes it somewhat difficult to say if hafnium or rhenium was discovered last. [66]

Applications

Much of the hafnium produced is used in the manufacture of control rods for nuclear reactors [34] and as an additive in nickel alloys to increase their heat resistance. [13]

Hafnium has limited technical applications due to a few factors. It is very similar to zirconium, a more abundant element that can be used in most cases, and pure hafnium wasn't widely available until the late 1950s, when it became a byproduct of the nuclear industry's need for hafnium-free zirconium. Additionally, hafnium is rare and difficult to separate from other elements, making it expensive. After the Fukushima disaster reduced the demand for hafnium-free zirconium, the price of hafnium increased significantly from around $500–$600/kg ($227-$272/lb) in 2014 to around $1000/kg ($454/lb) in 2015. [67] Hafnium products, such as tubes and sheets of the metal, could be purchased at €250/kg ($170/lb) in 2009. [13]

Nuclear reactors

The nuclei of several hafnium isotopes can each absorb multiple neutrons. This makes hafnium a good material for nuclear reactors' control rods. Its neutron capture cross section (Capture Resonance Integral Io ≈ 2000 barns) [68] is about 600 times that of zirconium (other elements that are good neutron-absorbers for control rods are cadmium and boron). Excellent mechanical properties and exceptional corrosion-resistance properties allow its use in the harsh environment of pressurized water reactors. [34] The German research reactor FRM II uses hafnium as a neutron absorber. [69] It is also common in military reactors, particularly in US naval submarine reactors, to slow reactor rates that are too high. [70] [71] It is seldom found in civilian reactors, the first core of the Shippingport Atomic Power Station (a conversion of a naval reactor) being a notable exception. [72]

Alloys

Hafnium-containing rocket nozzle of the Apollo Lunar Module in the lower right corner Apollo AS11-40-5866.jpg
Hafnium-containing rocket nozzle of the Apollo Lunar Module in the lower right corner

Hafnium is used in alloys with iron, titanium, niobium, tantalum, and other metals. An alloy used for liquid-rocket thruster nozzles, for example the main engine of the Apollo Lunar Modules, is C103 which consists of 89% niobium, 10% hafnium and 1% titanium. [73]

Small additions of hafnium increase the adherence of protective oxide scales on nickel-based alloys. It thereby improves the corrosion resistance, especially under cyclic temperature conditions that tend to break oxide scales, by inducing thermal stresses between the bulk material and the oxide layer. [74] [75] [76] An alloy that includes as little as 1% hafnium can withstand temperatures that are 50 °C (122 °F) higher than the same alloy without hafnium. [13]

Microprocessors

Hafnium-based compounds are employed in gates of transistors as insulators in the 45 nm (and below) generation of integrated circuits from Intel, IBM and others. [77] [78] Hafnium oxide-based compounds are practical high-k dielectrics, allowing reduction of the gate leakage current which improves performance at such scales. [79] [80] [81]

Isotope geochemistry

Isotopes of hafnium and lutetium are also used in isotope geochemistry and geochronological applications, in lutetium-hafnium dating. It is often used as a tracer of isotopic evolution of Earth's mantle through time. [82] This is because 176Lu decays to 176Hf with a half-life of approximately 37 billion years. [83] [84] [85]

In most geologic materials, zircon is the dominant host of hafnium (>10,000 ppm) and is often the focus of hafnium studies in geology. [86] Hafnium is readily substituted into the zircon crystal lattice, and is therefore very resistant to hafnium mobility and contamination. Zircon also has an extremely low Lu/Hf ratio, making any correction for initial lutetium minimal. Although the Lu/Hf system can be used to calculate a "model age", i.e. the time at which it was derived from a given isotopic reservoir such as the depleted mantle, these "ages" do not carry the same geologic significance as do other geochronological techniques as the results often yield isotopic mixtures and thus provide an average age of the material from which it was derived. [87] [88]

Garnet is another mineral that contains appreciable amounts of hafnium to act as a geochronometer. The high and variable Lu/Hf ratios found in garnet make it useful for dating metamorphic events. [89] Mass spectrometry also makes use of these ratios to date garnet formed through igneous events. [90]

Other uses

Due to its heat resistance and its affinity to oxygen and nitrogen, hafnium is a good scavenger for oxygen and nitrogen in gas-filled and incandescent lamps. Hafnium is also used as the electrode in plasma cutting because of its ability to shed electrons into the air. [91]

The high energy content of 178m2Hf was the concern of a DARPA-funded program in the US. This program eventually concluded that using the 178m2Hf nuclear isomer of hafnium to construct high-yield weapons with X-ray triggering mechanisms—an application of induced gamma emission—was infeasible because of its expense and difficulty to manufacture. [23] See hafnium controversy . [24]

Hafnium metallocene compounds can be prepared from hafnium tetrachloride and various cyclopentadiene-type ligand species. Perhaps the simplest hafnium metallocene is hafnocene dichloride. Hafnium metallocenes are part of a large collection of Group 4 transition metal metallocene catalysts that are used worldwide in the production of polyolefin resins like polyethylene and polypropylene. [92]

A pyridyl-amidohafnium catalyst can be used for the controlled iso-selective polymerization of propylene which can then be combined with polyethylene to make a much tougher recycled plastic. [93]

Hafnium diselenide is studied in spintronics thanks to its charge density wave and superconductivity. [94]

Toxicity and safety

Hafnium powder
Hazards
GHS labelling:
GHS-pictogram-flamme.svg
Danger
H228, H250
P210, P222, P231+P232, P233, P240, P370+P378 [95]
NFPA 704 (fire diamond)
[96]
NFPA 704.svgHealth 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g. sodium chlorideFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
4
0

Hafnium is a pyrophoric material, and as such fine particles can spontaneously combust upon exposure to air. Hafnium powder is often wetted with at least 25% water by weight to be considered safe - the metal is insoluble in water. [97] Machining hafnium is particularly hazardous because of the potential for fine particles of the metal to be produced and immediately introduced to frictional force. Compounds that contain this metal are rarely encountered by most people. [98] The pure metal is not considered toxic, though it has been observed to accumulate in the liver when injected into rats. [13] Hafnium compounds should be handled as if they were toxic because the ionic forms of metals are normally at greatest risk for toxicity, and limited animal testing has been done for hafnium compounds. [98] Hafnium tetrachloride and hafnium tetrabromide, which are often part of industrial processes that use the element, are of particular note, with both compounds releasing acidic fumes on contact with water (hydrochloric and hydrobromic acid, respectively). Additionally, hafnium tetrachloride has been observed as causing liver damage at high exposure levels. [13]

People can be exposed to hafnium in the workplace by breathing, swallowing, skin, and eye contact. In the United States, the Occupational Safety and Health Administration (OSHA) has set the legal limit (permissible exposure limit) for exposure to hafnium and hafnium compounds in the workplace as TWA 0.5 mg/m3 over an 8-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set the same recommended exposure limit (REL). [35] At levels of 50 mg/m3, hafnium is immediately dangerous to life and health. [99]

Because the mineral zircon is often associated with traces of the radioactive elements uranium and thorium, the chemically destructive processes used to separate zirconium from hafnium have potential to release these radioactive elements and their decay products into the environment along with other reaction wastes. Additionally, synthesis pathways that involve liquid-liquid extraction introduce ammonium chloride and sulfate into reaction mixtures, which as effluent can reduce available oxygen in water sources or produce cyanides if it comes into contact with thiocyanate-containing compounds. [13]

References

  1. ↑ "Standard Atomic Weights: Hafnium". CIAAW. 2019.
  2. ↑ Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (2022-05-04). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN   1365-3075.
  3. 1 2 Arblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN   978-1-62708-155-9.
  4. ↑ Hf(–2) occurs in Hf(CO)62−; see John E. Ellis (2003). "Metal Carbonyl Anions: from [Fe(CO)4]2− to [Hf(CO)6]2− and Beyond†". Organometallics. 22 (17): 3322–3338. doi:10.1021/om030105l.
  5. ↑ Hf(0) occur in (η6-(1,3,5-tBu)3C6H3)2Hf and [(η5-C5R5Hf(CO)4]−, see Chirik, P. J.; Bradley, C. A. (2007). "4.06 - Complexes of Zirconium and Hafnium in Oxidation States 0 to ii". Comprehensive Organometallic Chemistry III. From Fundamentals to Applications. Vol. 4. Elsevier Ltd. pp. 697–739. doi:10.1016/B0-08-045047-4/00062-5. ISBN   978-0-08-045047-6.
  6. ↑ Hf(I) has been observed in hafnium monobromide (HfBr), see Marek, G.S.; Troyanov, S.I.; Tsirel'nikov, V.I. (1979). "Кристаллическое строение и термодинамические характеристики монобромидов циркония и гафния / Crystal structure and thermodynamic characteristics of monobromides of zirconium and hafnium". Журнал неорганической химии / Russian Journal of Inorganic Chemistry (in Russian). 24 (4): 890–893.
  7. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 28. doi:10.1016/C2009-0-30414-6. ISBN   978-0-08-037941-8.
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