Zirconium

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40 yttriumzirconiumniobium
Ti

Zr

Hf
Periodic Table - Extended Periodic Table
General
Name, Symbol, Number zirconium, Zr, 40
Chemical series transition metals
Group, Period, Block 4, 5, d
Appearance silvery white
Standard atomic weight 91.224(2)  g·mol−1
Electron configuration [Kr] 4d2 5s2
Electrons per shell 2, 8, 18, 10, 2
Physical properties
Phase solid
Density (near r.t.) 6.52  g·cm−3
Liquid density at m.p. 5.8  g·cm−3
Melting point 2128 K
(1855 °C, 3371 °F)
Boiling point 4682 K
(4409 °C, 7968 °F)
Heat of fusion 14  kJ·mol−1
Heat of vaporization 573  kJ·mol−1
Heat capacity (25 °C) 25.36  J·mol−1·K−1
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
at T(K) 2639 2891 3197 3575 4053 4678
Atomic properties
Crystal structure hexagonal
Oxidation states 4
(amphoteric oxide)
Electronegativity 1.33 (scale Pauling)
Ionization energies
(more)
1st:  640.1  kJ·mol−1
2nd:  1270  kJ·mol−1
3rd:  2218  kJ·mol−1
Atomic radius 155  pm
Atomic radius (calc.) 206  pm
Covalent radius 148  pm
Miscellaneous
Magnetic ordering no data
Electrical resistivity (20 °C) 421 n Ω·m
Thermal conductivity (300 K) 22.6  W·m−1·K−1
Thermal expansion (25 °C) 5.7  µm·m−1·K−1
Speed of sound (thin rod) (20 °C) 3800 m/s
Young's modulus 68  GPa
Shear modulus 33  GPa
Poisson ratio 0.34
Mohs hardness 5.0
Vickers hardness 903  MPa
Brinell hardness 650  MPa
CAS registry number 7440-67-7
Selected isotopes
Main article: Isotopes of zirconium
iso NA half-life DM DE (MeV) DP
88Zr syn 83.4 d ε - 88Y
γ 0.392D -
89Zr syn 78.4 h ε - 89Y
β+ 0.902 89Y
γ 0.909D -
90Zr 51.45% Zr is stable with 50 neutrons
91Zr 11.22% Zr is stable with 51 neutrons
92Zr 17.15% Zr is stable with 52 neutrons
93Zr syn 1.53×106y β- 0.060 93Nb
94Zr 17.38% Zr is stable with 54 neutrons
96Zr 2.8% >3.9×1020y β-β-  ? 96Mo
References

Zirconium (IPA: /zəˈkəʊniəm, ˌzɛːˈkəʊniəm, zɜːɹ'kəʊniəm) is a chemical element that has the symbol Zr and has the atomic number 40. A lustrous, very corrosion resistant, gray-white, strong transition metal that resembles titanium, zirconium is obtained mainly from the mineral zircon. Zirconium is primarily used in nuclear reactors, especially in the cladding of the fuel rods, due to its low neutron-capture cross-section and its resistance to corrosion.

Contents

  • 1 Characteristics
  • 2 Applications
    • 2.1 Other uses
    • 2.2 Hafnium-free zirconium
  • 3 History
  • 4 Occurrence
  • 5 Isotopes
  • 6 Compounds
  • 7 Precautions
  • 8 References
  • 9 External links

[edit] Characteristics

Zirconium is a grayish-white metal, lustrous, and quite corrosion-resistant. Zirconium is lighter than steel and its hardness is similar to copper. When it is finely divided into a powder, zirconium can spontaneously ignite in air, especially at high temperatures. (It is much more difficult to ignite the solid metal.) The Zirconium-zinc alloy becomes magnetic at temperatures below 35 K. The oxidation state of zirconium is usually +4, although +3 and +2 can also be obtained in chemical compounds.

[edit] Applications

Cubic zirconia, ZrO2

The major end-uses of the mineral zircon (ZrSiO4) are refractories, foundry sands (including investment casting) and ceramic opacification. Zircon is also marketed as a natural gemstone used in jewelry. Zirconium oxide is processed to produce cubic zirconia. This forms a brilliant clear crystal used as a low-cost substitute for diamond.

[edit] Other uses

In 2007, zirconium costs about $150/kg.

[edit] Hafnium-free zirconium

Nuclear reactor-grade zirconium alloys must be made of purified zirconium - free of hafnium contamination, since hafnium has very high neutron absorption cross-section, 600 times higher than zirconium's. Commercial zirconium naturally contains 1-5% of hafnium which must be removed. This removal process is difficult. (Zirconium and hafnium are two of the most difficult elements to separate.) Two main process are in use: liquid-liquid extraction, exploiting the difference of solubility of metal thiocyanates in methyl isobutyl ketone, used mainly in United States; and extractive distillation, used primarily in Europe. The resulting reactor-grade zirconium is about 10 times as expensive as the hafnium-contaminated commercial grade. The separated hafnium is used for nuclear-reactor control rods. The zirconium is mostly used in an almost pure state, in the form of "low" alloys, most often from the zircaloy group.

[edit] History

Zirconium (Arabic zarkûn from Persian zargûn زرگون meaning "gold like") was discovered in 1789 by Martin Heinrich Klaproth, and it was isolated in 1824 by Jöns Jakob Berzelius.

The zirconium-containing mineral zircon, or its variations (jargon, hyacinth, jacinth, or ligure), were mentioned in biblical writings. The mineral was not known to contain a new element until Klaproth analyzed a jargon from the island of Ceylon in the Indian Ocean. He named the new element Zirkonertz (zirconia). The impure metal was isolated first by Berzelius by heating a mixture of potassium and potassium-zirconium fluoride in a small decomposition process conducted in an iron tube. Pure zirconium wasn't prepared until 1914.

The crystal bar process (or Iodide process), discovered by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925, was the first industrial process for the commercial production of pure metallic zirconium. It was later superseded by the Kroll process.

[edit] Occurrence

Zirconium output in 2005
World production trend of zirconium mineral concentrates

Zirconium is never found in nature as a native metal. The principal economic source of zirconium is the zirconium silicate mineral, zircon (ZrSiO4), which is found in deposits located in Australia, South Africa and the United States, as reported by the British Geological Survey. It is extracted either as a dark sooty powder, or as a gray metallic crystalline substance. Zirconium and hafnium are contained in zircon at a ratio of about 50 to 1, and they are quite difficult to separate chemically. Zircon is a co-product or by-product of the mining and processing of heavy-mineral sands for the titanium minerals, ilmenite and rutile, or from tin minerals. Zirconium also occurs in about 30 other recognized mineral species including baddeleyite. This metal is commercially produced mostly by the reduction of the zirconium(IV) chloride with magnesium metal in the Kroll process. Commercial-quality zirconium for most uses still has a content of 1% to 3% hafnium.

This element is relatively-abundant in S-type stars, and it has been detected in the sun and in meteorites. Lunar rock samples brought back from several Apollo program missions to the moon have a quite high zirconium oxide content relative to terrestrial rocks.

See also zirconium minerals.

[edit] Isotopes

Main article: isotopes of zirconium

Naturally-occurring zirconium is composed of four stable isotopes, and one extremely long-lived radioisotope (96Zr). The second most stable radioisotope is 93Zr which has a half-life of 1.53 million years. Eighteen other radioisotopes have been observed. Most of these have half-lives that are less than a day except for 95Zr (64.02 days), 88Zr (63.4 days), and 89Zr (78.41 hours). The primary decay mode is electron capture for isotopes lighter than 92Zr, and the primary mode for heavier isotopes is beta decay.

[edit] Compounds

Some common zirconium compunds are: ZrC, ZrO2, ZrN, ZrCl4, ZrS2, ZrSi2, ZrSiO4, ZrF4, ZrBr4, ZrI4, Zr(OH)4, C10H11ClZr, Zr(CH3CH2COO)4, Zr(WO4)2, ZrH2, Pb(ZrxTi1-x)O3

[edit] Precautions

Zirconium rod

Compounds containing zirconium are not noted for toxicity. The metal dust can ignite in air and should be regarded as a major fire and explosion hazard. Zirconium has no known biological role.