Zirconium 1

Zirconium
Zirconium

Appearance

silvery white

General properties

Name, symbol, number zirconium, Zr, 40

Pronunciation English pronunciation: /zərˈkoʊniəm/ zər-KOH-ni-əm

Element category transition metal

Group, period, block 4, 5, d

Standard atomic weight 91.224 g·mol

−1

Electron configuration [Kr] 5s 4d

2 2

Electrons per shell 2, 8, 18, 10, 2 (Image)

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

Specific heat capacity (25 °C) 25.36 J·mol−1·K−1

Vapor pressure

P/Pa 1 10 100 1k 10 k 100 k

at 2639 2891 3197 3575 4053 4678

T/K

Atomic properties

Oxidation states [1]

4, 3, 2, 1,
(amphoteric oxide)

Electronegativity 1.33 (Pauling scale)

Zirconium 2

Ionization energies 1st: 640.1 kJ·mol−1

2nd: 1270 kJ·mol−1

3rd: 2218 kJ·mol−1

Atomic radius 160 pm

Covalent radius 175±7 pm

Miscellanea

Crystal structure hexagonal close-packed

Magnetic ordering [2]

paramagnetic

Electrical resistivity (20 °C) 421 nΩ·m

Thermal conductivity (300 K) 22.6 W·m−1·K−1

Thermal expansion (25 °C) 5.7 µm·m ·K

−1 −1

Speed of sound (thin rod) (20 °C) 3800 m/s

Young's modulus 88 GPa

Shear modulus 33 GPa

Bulk modulus 91.1 GPa

Poisson ratio 0.34

Mohs hardness 5.0

Vickers hardness 903 MPa

Brinell hardness 650 MPa

CAS registry number 7440-67-7

Most stable isotopes

Main article: Isotopes of zirconium

Zirconium 3

iso NA half-life DM DE DP
(MeV)
88
Zr syn 83.4 d ε - 88
Y

γ 0.392D -
89
Zr syn 78.4 h ε - 89
Y

β+ 0.902 89
Y

γ 0.909D -
90
Zr 51.45% 90
Zr is stable with 50 neutron

91
Zr 11.22% 91
Zr is stable with 51 neutron

92
Zr 17.15% 92
Zr is stable with 52 neutron

93
Zr trace 1.53×10 y
6
β
− 0.060 93
Nb
94
Zr 17.38% 1.1×10 y
17 − −
β β - 94
Mo

96 2.8% 19 [3] − − 3.348 96

Zr 2.0×10 y β β Mo

Zirconium (pronounced /zərˈkoʊniəm/ zər-KOH-ni-əm) is a chemical element with the symbol Zr and atomic
number 40. Its atomic mass is 91.224. It is a lustrous, grey-white, strong transition metal that resembles titanium.
Zirconium is used as an alloying agent for its strong resistance to corrosion. It is never found as a native metal; it is
obtained mainly from the mineral zircon, which can be purified with chlorine. Zirconium was first isolated in an
impure form in 1824 by Jöns Jakob Berzelius.
Zirconium has no known biological role. Zirconium forms both inorganic and organometallic compounds such as
zirconium dioxide and zirconocene dichloride, respectively. There are five naturally occurring isotopes, three of
which are stable. Short-term exposure to zirconium powder causes minor irritation, and inhalation of zirconium
compounds can cause skin and lung granulomas.

Characteristics
Zirconium is a lustrous, grayish-white, soft, ductile, and malleable metal which is solid at room temperature, though
it becomes hard and brittle at lower purities.[4] [5] In powder form, zirconium is highly flammable, but the solid form
is far less prone to ignition. Zirconium is highly resistant to corrosion by alkalis, acids, salt water, and other
agents.[6] However, it will dissolve in hydrochloric and sulfuric acid, especially when fluorine is present.[7] Alloys
with zinc become magnetic below 35 K.[6]
Zirconium's melting point is at 1855°C, and its boiling point 4409°C.[6] Zirconium has an electronegativity of 1.33
on the Pauling scale. Of the elements within d-block, zirconium has the fourth lowest electronegativity after yttrium,
lutetium, and hafnium.[8]
Zirconium 4

Applications
Because of zirconium's excellent resistance to corrosion, it is often used as an alloying agent in materials that are
exposed to corrosive agents, such as surgical appliances, explosive primers, vacuum tube getters and filaments.
Zirconium dioxide (ZrO2) is used in laboratory crucibles, metallurgical furnaces, as a refractory material,[6] and it
can be sintered into a ceramic knife. Zircon (ZrSiO4) is cut into gemstones for use in jewelry. Zirconium carbonate
(3ZrO2·CO2·H2O) was used in lotions to treat poison ivy, but this was discontinued because it occasionally caused
bad skin reactions.[4]
Ninety percent of all zirconium produced is used in nuclear reactors (in the form of zircaloys) because of its low
neutron-capture cross-section and resistance to corrosion.[5] [6] Zirconium alloys are used in space vehicle parts for
their resistance to heat, an important quality given the extreme heat associated with atmospheric reentry.[9]
Zirconium is also a component in some abrasives, such as grinding wheels and sandpaper.[10] Zirconium is used in
weapons such as the BLU-97/B Combined Effects Bomb for incendiary effect.
High temperature parts such as combustors, blades and vanes in modern jet engines and stationary gas turbines are to
an ever increasing extent being protected by thin ceramic layers which reduce the metal temperatures below and
keep them from undergoing (too) extensive deformation which could possibly result in early failure. They are
absolutely necessary for the most modern gas turbines which are driven to ever higher firing temperatures to produce
more electricity at less CO2. These ceramic layers are usually composed by a mixture of zirconium and yttrium
oxide.[11]

Refining
Upon being collected from coastal waters, the solid mineral zircon is purified by spiral concentrators to remove
excess sand and gravel and by magnetic separators to remove ilmenite and rutile. The byproducts can then be
dumped back into the water safely, as they are all natural components of beach sand. The refined zircon is then
purified into pure zirconium by chlorine or other agents, then sintered until sufficiently ductile for metalworking.[5]
Zirconium and hafnium are both contained in zircon and they are quite difficult to separate due to their extremely
similar chemical properties.[9] Usually, an ion exchange process is used to separate them.

History
The zirconium-containing mineral zircon, or its variations (jargoon, hyacinth, jacinth, ligure), were mentioned in
biblical writings.[6] [9] The mineral was not known to contain a new element until 1789,[10] when Klaproth analyzed
a jargoon from the island of Sri Lanka in the Indian Ocean. He named the new element Zirkonerde (zirconia).[6]
Humphry Davy attempted to isolate this new element in 1808 through electrolysis, but failed.[4] Zirconium (from
Syriac ‫ ܥܢܥܓܪܐܙ‬zargono,[12] Arabic zarkûn ‫ ىعنقشئ‬from Persian zargûn ‫ نوگرز‬meaning "gold like")[9] was first
isolated in an impure form in 1824 by Berzelius by heating a mixture of potassium and potassium-zirconium fluoride
in a small decomposition process conducted in an iron tube.[6] These words were adapted into German Zirkon which
became the source of the English words: Zircon and Zirconium. [13]
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. The process
involved thermally decomposing zirconium tetraiodide. It was superseded in 1945 by the much cheaper Kroll
process developed by William Justin Kroll, in which zirconium tetrachloride is broken down by magnesium.[5] [14]
Zirconium 5

Occurrence

Geological
Zirconium has a concentration of about 130 mg/kg within the earth's
crust and about 0.026 μg/L in sea water,[15] though it is never found in
nature as a native metal. The principal commercial source of zirconium
is the zirconium silicate mineral, zircon (ZrSiO4),[4] which is found
primarily in Australia, Brazil, India, Russia, South Africa, and the
United States, as well as in smaller deposits around the world.[5] 80% Zirconium output in 2005
of zircon mining occurs in Australia and South Africa.[4] Zircon
resources exceed 60 million metric tons worldwide[16] and annual
worldwide zirconium production is approximately 900,000 metric
tons.[15]

Zircon is a by-product of the mining and processing of the titanium

minerals ilmenite and rutile, as well as tin mining.[17] From 2003 to
2007, zircon prices have steadily increased from $360 to $840 per
metric ton.[16] Zirconium also occurs in more than 140 other
recognized mineral species including baddeleyite and kosnarite.[18]
This metal is commercially produced mostly by the reduction of the World production trend of zirconium mineral
zirconium(IV) chloride with magnesium metal in the Kroll process.[6] concentrates

Commercial-quality zirconium for most uses still has a content of 1%

to 3% hafnium.[4]

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.[6]

Biological
Zirconium has no known biological role, though zirconium salts are of low toxicity. The human body contains, on
average, only 1 milligram of zirconium, and daily intake is approximately 50 μg per day. Zirconium content in
human blood is as low as 10 parts per billion. Aquatic plants readily take up soluble zirconium, but it is rare in land
plants. 70% of plants have no zirconium content at all, and those that do have as little as 5 parts per billion.[4]

Compounds
As a transition metal, zirconium forms various inorganic compounds, such as zirconium dioxide (ZrO2). This
compound, also referred to as zirconia, has exceptional fracture toughness and chemical resistance, especially in its
cubic form.[19] These properties make zirconia useful as a thermal barrier coating,[20] though it is also a common
diamond substitute.[19] Zirconium tungstate is an unusual substance in that it shrinks in all directions when heated,
whereas most other substances expand when heated.[6] ZrZn2 is one of only two substances to exhibit
superconductivity and ferromagnetism simultaneously, with the other being UGe2.[21] Other inorganic zirconium
compounds include zirconium(II) hydride, zirconium nitride, and zirconium tetrachloride (ZrCl4), which is used in
the Friedel-Crafts reaction.[22]
Organozirconium chemistry is the study of compounds containing a carbon-zirconium bond. These organozirconium
compounds are often employed as polymerization catalysts. The first such compound was zirconocene dibromide,
prepared in 1952 by John M. Birmingham at Harvard University.[23] Schwartz's reagent, prepared in 1970 by P. C.
Wailes and H. Weigold,[24] is a metallocene used in organic synthesis for transformations of alkenes and alkynes.[25]
Zirconium 6

Isotopes
Naturally occurring zirconium is composed of five isotopes. 90Zr, 91Zr,
and 92Zr are stable. 94Zr has a half-life of 1.10×1017 years. 96Zr has a
half-life of 2.4×1019 years, making it the longest-lived radioisotope of
zirconium. Of these natural isotopes, 90Zr is the most common, making
up 51.45% of all zirconium. 96Zr is the least common, comprising only
2.80% of zirconium.[26]

28 artificial isotopes of zirconium have been synthesized, ranging in

atomic mass from 78 to 110. 93Zr is the longest-lived artificial isotope,
with a half-life of 1.53×106 years. 110Zr, the heaviest isotope of
A zirconium rod
zirconium, is also the shortest-lived, with an estimated half-life of only
30 milliseconds. Radioactive isotopes at or above mass number 93
decay by β−, whereas those at or below 89 decay by β+. The only exception is 88Zr, which decays by ε.[26]

Zirconium also has six metastable isomers: 83mZr, 85mZr, 89mZr, 90m1Zr, 90m2Zr, and 91mZr. Of these, 90m2Zr has the
shortest half-life at 131 nanoseconds. 89mZr is the longest lived with a half-life of 4.161 minutes.[26]

Toxicity
Short-term exposure to zirconium powder can cause irritation, but only contact with the eyes requires medical
attention.[27] Inhalation of zirconium compounds can cause skin and lung granulomas. Zirconium aerosols can cause
pulmonary granulomas. Persistent exposure to zirconium tetrachloride resulted in increased mortality in rats and
guinea pigs and a decrease of blood hemoglobin and red blood cells in dogs. OSHA recommends a 5 mg/m3 time
weighted average limit and a 10 mg/m3 short-term exposure limit.[28]

See also
• Zirconium compounds
• Zirconium minerals

External links
• WebElements.com: Zirconium [29]
• Chemistry in its element podcast [30] (MP3) from the Royal Society of Chemistry's Chemistry World: Zirconium
[31]

References
[1] "Zirconium: zirconium(I) fluoride compound data" (http:/ / openmopac. net/ data_normal/ zirconium(i) fluoride_jmol. html).
OpenMOPAC.net. . Retrieved 2007-12-10.
[2] Magnetic susceptibility of the elements and inorganic compounds (http:/ / www-d0. fnal. gov/ hardware/ cal/ lvps_info/ engineering/
elementmagn. pdf), in Handbook of Chemistry and Physics 81st edition, CRC press.
[3] Pritychenko, Boris; V. Tretyak. "Adopted Double Beta Decay Data" (http:/ / www. nndc. bnl. gov/ bbdecay/ list. html). National Nuclear
Data Center. . Retrieved 2008-02-11.
[4] Emsley, John (2001). Nature's Building Blocks. Oxford: Oxford University Press. pp. 506–510. ISBN 0-19-850341-5.
[5] "Zirconium" (http:/ / www. madehow. com/ Volume-1/ Zirconium. html). How Products Are Made. Advameg Inc.. 2007. . Retrieved
2008-03-26.
[6] Lide, David R., ed (2007–2008). "Zirconium". CRC Handbook of Chemistry and Physics. 4. New York: CRC Press. p. 42.
ISBN 978-0-8493-0488-0.
[7] Considine, Glenn D., ed (2005). "Zirconium". Van Nostrand's Encyclopedia of Chemistry. New York: Wylie-Interscience. pp. 1778–1779.
ISBN 0-471-61525-0.
Zirconium 7

[8] Winter, Mark (2007). "Electronegativity (Pauling)" (http:/ / www. webelements. com/ webelements/ properties/ text/ image-flash/
electroneg-pauling. html). University of Sheffield. . Retrieved 2008-03-05.
[9] Stwertka, Albert (1996). A Guide to the Elements. Oxford University Press. pp. 117–119. ISBN 0-19-508083-1.
[10] Krebs, Robert E. (1998). The History and Use of our Earth's Chemical Elements. Westport, Connecticut: Greenwood Press. pp. 98–100.
ISBN 0-313-30123-9.
[11] Meier, S. M.; Gupta, D. K. (1994). "The Evolution of Thermal Barrier Coatings in Gas Turbine Engine Applications". Journal of
Engineering for Gas Turbines and Power 116: 250. doi:10.1115/1.2906801.
[12] Pearse, Roger (2002-09-16). "Syriac Literature" (http:/ / www. tertullian. org/ rpearse/ oriental/ syriac. htm). . Retrieved 2008-02-11.
[13] http:/ / www. etymonline. com/ index. php?term=zircon
[14] Hedrick, James B. (1998). "Zirconium" (http:/ / minerals. usgs. gov/ minerals/ pubs/ metal_prices/ metal_prices1998. pdf) (PDF). Metal
Prices in the United States through 1998. US Geological Survey. pp. 175–178. . Retrieved 2008-02-26.
[15] Peterson, John; MacDonell, Margaret (2007). "Zirconium" (http:/ / www. evs. anl. gov/ pub/ doc/
ANL_ContaminantFactSheets_All_070418. pdf) (PDF). Radiological and Chemical Fact Sheets to Support Health Risk Analyses for
Contaminated Areas. Argonne National Laboratory. pp. 64–65. . Retrieved 2008-02-26.
[16] "Zirconium and Hafnium" (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/ zirconium/ mcs-2008-zirco. pdf) (PDF). Mineral
Commodity Summaries (US Geological Survey): 192–193. January 2008. . Retrieved 2008-02-24.
[17] Callaghan, R. (2008-02-21). "Zirconium and Hafnium Statistics and Information" (http:/ / minerals. usgs. gov/ minerals/ pubs/ commodity/
zirconium/ ). US Geological Survey. . Retrieved 2008-02-24.
[18] Ralph, Jolyon; Ida Ralph (2008). "Minerals that include Zr" (http:/ / www. mindat. org/ chemsearch. php?inc=Zr,& exc=& sub=Search+
for+ Minerals). Mindat.org. . Retrieved 2008-02-23.
[19] "Zirconia" (http:/ / www. azom. com/ details. asp?ArticleID=133#_Key_Properties). AZoM.com. 2008. . Retrieved 2008-03-17.
[20] Gauthier, V.; Dettenwanger, F.; Schütze, M. (2002-04-10). "Oxidation behavior of γ-TiAl coated with zirconia thermal barriers".
Intermetallics (Frankfurt, Germany: Karl Winnacker Institut der Dechema) 10 (7): 667–674. doi:10.1016/S0966-9795(02)00036-5.
[21] Day, Charles (September 2001). "Second Material Found that Superconducts in a Ferromagnetic State". Physics Today (American Institute
of Physics) 54 (9): 16. doi:10.1063/1.1420499.
[22] Bora U. (2003). "Zirconium Tetrachloride". Synlett: 1073–1074. doi:10.1055/s-2003-39323.
[23] Rouhi, A. Maureen (2004-04-19). "Organozirconium Chemistry Arrives" (http:/ / pubs. acs. org/ cen/ nlw/ 8216sci1. html). Science &
Technology (Chemical & Engineering News) 82 (16): 36–39. ISSN 0009-2347. . Retrieved 2008-03-17.
[24] Wailes, P. C. and Weigold, H. (1970). "Hydrido complexes of zirconium I. Preparation". Journal of Organometallic Chemistry 24: 405–411.
doi:10.1016/S0022-328X(00)80281-8.
[25] Hart, D. W. and Schwartz,J. (1974). "Hydrozirconation. Organic Synthesis via Organozirconium Intermediates. Synthesis and
Rearrangement of Alkylzirconium(IV) Complexes and Their Reaction with Electrophiles". J. Am. Chem. Soc. 96 (26): 8115–8116.
doi:10.1021/ja00833a048.
[26] Audi, G (2003). "Nubase2003 Evaluation of Nuclear and Decay Properties". Nuclear Physics A (Atomic Mass Data Center) 729: 3–128.
doi:10.1016/j.nuclphysa.2003.11.001.
[27] "Zirconium" (http:/ / www. oit. org/ public/ english/ protection/ safework/ cis/ products/ icsc/ dtasht/ _icsc14/ icsc1405. htm). International
Chemical Safety Cards. International Labour Organization. October 2004. . Retrieved 2008-03-30.
[28] "Zirconium Compounds" (http:/ / www. cdc. gov/ niosh/ pel88/ 7440-67. html). National Institute for Occupational Health and Safety.
2007-12-17. . Retrieved 2008-02-17.
[29] http:/ / webelements. com/ zirconium/
[30] http:/ / www. rsc. org/ chemistryworld/ podcast/ element. asp
[31] http:/ / www. rsc. org/ images/ CIIE_zirconium_remix2_48k_tcm18-117340. mp3
Article Sources and Contributors 8

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