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Ni

Pd
Appearance
lustrous, metallic, and silvery with a gold tinge
General properties
Name, symbol, number nickel, Ni, 28
Element category transition metal
Group, period, block 104, d
Standard atomic weight 58.6934(2)g·mol−1
Electron configuration [Ar] 4s1 3d9
Electrons per shell 2, 8, 17, 1 (Image)
Physical properties
Phase solid
Density (near r.t.) 8.908 g·cm−3
Liquid density at m.p. 7.81 g·cm−3
Melting point 1728 K, 1453 °C, 2651 °F
Boiling point 3186 K, 2732 °C, 5275 °F
Heat of fusion 17.48 kJ·mol−1
Heat of vaporization 377.5 kJ·mol−1
Specific heat capacity (25 °C) 26.07 J·mol−1·K−1
Vapor pressure
P/Pa 1 10 100 1 k 10 k 100 k
at T/K 1783 1950 2154 2410 2741 3184
Atomic properties
Oxidation states 4[1], 3, 2, 1 [2], -1
(mildly basic oxide)
Electronegativity 1.91 (Pauling scale)
Ionization energies
(more)
1st: 737.1 kJ·mol−1
2nd: 1753.0 kJ·mol−1
3rd: 3395 kJ·mol−1
Atomic radius 124 pm
Covalent radius 124±4 pm
Van der Waals radius 163 pm
Miscellanea
Crystal structure face-centered cubic
Magnetic ordering ferromagnetic
Electrical resistivity (20 °C) 69.3 nΩ·m
Thermal conductivity (300 K) 90.9 W·m−1·K−1
Thermal expansion (25 °C) 13.4 µm·m−1·K−1
Speed of sound (thin rod) (r.t.) 4900 m·s−1
Young's modulus 200 GPa
Shear modulus 76 GPa
Bulk modulus 180 GPa
Poisson ratio 0.31
Mohs hardness 4.0
Vickers hardness 638 MPa
Brinell hardness 700 MPa
CAS registry number 7440-02-0
Most stable isotopes
Main article: Isotopes of nickel
iso NA half-life DM DE (MeV) DP
56Ni syn 6.075 d ε - 56Co
γ 0.158, 0.811 -
58Ni 68.077% 58Ni is stable with 30 neutrons
59Ni trace 76000 y ε - 59Co
60Ni 26.233% 60Ni is stable with 32 neutrons
61Ni 1.14% 61Ni is stable with 33 neutrons
62Ni 3.634% 62Ni is stable with 34 neutrons
63Ni syn 100.1 y β 0.0669 63Cu
64Ni 0.926% 64Ni is stable with 36 neutrons

Nickel (pronounced /ˈnɪkəl/) is a chemical element, with the chemical symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. It is one of the four ferromagnetic elements at about room temperature, the other three being iron, cobalt and gadolinium. Its use has been traced as far back as 3500 BC, but it was first isolated and classified as a chemical element in 1751 by Axel Fredrik Cronstedt, who initially mistook its ore for a copper mineral. Its most important ore minerals are laterites, including limonite and garnierite, and pentlandite. Major production sites include Sudbury region in Canada, New Caledonia and Norilsk in Russia. The metal is corrosion-resistant, finding many uses in alloys, as a plating, in the manufacture of coins, magnets and common household utensils, as a catalyst for hydrogenation, and in a variety of other applications. Enzymes of certain life-forms contain nickel as an active center, which makes the metal an essential nutrient for those life forms.

Contents

Properties

Atomic

The electronic configuration of isolated nickel atom is counterintuitive: direct investigation[3] finds that the predominant electron structure of nickel is [Ar] 4s1 3d9, which is the more stable form because of relativistic effects. Whereas Hund's rule, which works well for most other elements, predicts an electron shell structure of [Ar] 3d8 4s2 (the symbol [Ar] refers to the argon-like core structure). This latter configuration is found in many chemistry textbooks and is also written as [Ar] 4s2 3d8, to emphasize that the 3d shell is the electron shell being filled by the highest-energy electrons.

Physical

Nickel is a silvery-white metal with a slight golden tinge that takes a high polish. It is one of only four elements that are magnetic at or near room temperature. Its Curie temperature is 355 °C. That is, nickel is non-magnetic above this temperature.[4] The unit cell of nickel is a face centered cube with the lattice parameter of 0.352 nm giving an atomic radius of 0.124 nm. Nickel belongs to the transition metals and is hard and ductile. It occurs most often in combination with sulfur and iron in pentlandite, with sulfur in millerite, with arsenic in the mineral nickeline, and with arsenic and sulfur in nickel galena.[5] Nickel is commonly found in iron meteorites as the alloys kamacite and taenite. Similar to the elements chromium, aluminium and titanium, nickel is a very reactive element, but is slow to react in air at normal temperatures and pressures due to the formation of a protective oxide surface. Due to its permanence in air and its slow rate of oxidation, it is used in coins, for plating metals such as iron and brass, for chemical apparatus, and in certain alloys such as German silver.

Nickel is chiefly valuable for the alloys it forms, especially many superalloys, and particularly stainless steel. Nickel is also a naturally magnetostrictive material, meaning that in the presence of a magnetic field, the material undergoes a small change in length.[6] In the case of nickel, this change in length is negative (contraction of the material), which is known as negative magnetostriction and is on the order of 50 ppm. Nickel is also used as a binder in the cemented tungsten carbide or hardmetal industry and used in proportions of six to 12% by weight. Nickel can make the tungsten carbide magnetic and adds corrosion-resistant properties to the cemented tungsten carbide parts, although the hardnesses are lower than parts made of the binder cobalt.[7]

Isotopes

Naturally occurring nickel is composed of 5 stable isotopes; 58Ni, 60Ni, 61Ni, 62Ni and 64Ni with 58Ni being the most abundant (68.077% natural abundance). 62Ni is the most stable known nuclide of all the existing elements, even exceeding the stability of 56Fe. 18 radioisotopes have been characterised with the most stable being 59Ni with a half-life of 76,000 years, 63Ni with a half-life of 100.1 years, and 56Ni with a half-life of 6.077 days. All of the remaining radioactive isotopes have half-lives that are less than 60 hours and the majority of these have half-lives that are less than 30 seconds. This element also has 1 meta state.[8]

Nickel-56 is produced in large quantities in type Ia supernovae and the shape of the light curve of these supernovae corresponds to the decay via beta radiation of nickel-56 to cobalt-56 and then to iron-56. Nickel-59 is a long-lived cosmogenic radionuclide with a half-life of 76,000 years. 59Ni has found many applications in isotope geology. 59Ni has been used to date the terrestrial age of meteorites and to determine abundances of extraterrestrial dust in ice and sediment. Nickel-60 is the daughter product of the extinct radionuclide 60Fe, which decays with a half-life of 2.6 million years. Because 60Fe has such a long half-life, its persistence in materials in the solar system at high enough concentrations may have generated observable variations in the isotopic composition of 60Ni. Therefore, the abundance of 60Ni present in extraterrestrial material may provide insight into the origin of the solar system and its early history. Nickel-62 has the highest binding energy per nucleon of any isotope for any element (8.7946 Mev/nucleon).[9] Isotopes heavier than 62Ni cannot be formed by nuclear fusion without losing energy. Nickel-48, discovered in 1999, is the most proton-rich heavy element isotope known. With 28 protons and 20 neutrons 48Ni is "double magic" (like 208Pb) and therefore unusually stable.[10][8]

The isotopes of nickel range in atomic weight from 48 u (48Ni) to 78 u (78Ni). Nickel-78's half-life was recently measured to be 110 milliseconds and is believed to be an important isotope involved in supernova nucleosynthesis of elements heavier than iron.[11]

Chemical

Nickel sulfate crystals
Tetracarbonyl nickel

The most common oxidation state of nickel is +2, but compounds of Ni0, Ni+, and Ni3+ are well known, and Ni4+ has been demonstrated.[12]

Nickel(0)

Tetracarbonylnickel (Ni(CO)4), discovered by Ludwig Mond,[12] is a volatile liquid at room temperature. On heating, the complex decomposes back to nickel and carbon monoxide:

Ni(CO)4 \overrightarrow{\leftarrow} Ni + 4 CO

This behavior is exploited in the Mond process for purifying nickel, as described above.[13] The related nickel(0) complex bis(cyclooctadiene)nickel(0) is a useful catalyst in organonickel chemistry due to the easily displaced cod ligands.

Nickel(II)

Nickel(II) compounds are known with all common anions, i.e. the sulfide, sulfate, carbonate, hydroxide, carboxylates, and halides. Nickel(II) sulfate is produced in large quantities by dissolving nickel metal or oxides in sulfuric acid. It exists as both a hexa- and heptahydrates.[14] This compound is useful for electroplating nickel. The four halogens form nickel compounds, all of which adopt octahedral geometries. chloride is of particular significance, and its behavior is illustrative of the other halides. Nickel(II) chloride is produced by dissolving nickel residues in hydrochloric acid. The dichloride is usually encountered as the green hexahydrate, but it can be dehydrated to give the yellow anhydrous NiCl2. Some tetracoordinate nickel(II) complexes form both tetrahedral and square planar geometries. The tetrahdral complexes are paramagnetic and the square planar complexes are diamagnetic. This equilibrium as well as the formation of octahedral complexes contrasts with the bahavior of the divalent complexes of the heavier group 10 metals, palladium(II) and platinum(II), which tend to adopt only square-planar complexes.[12]

Nickel(III)

Nickel(III) oxide is used as the cathode in many rechargeable batteries, including nickel-cadmium, nickel-iron, nickel hydrogen, and nickel-metal hydride, and used by certain manufacturers in Li-ion batteries.[15]

History

Because the ores of nickel are easily mistaken for ores of silver, understanding of this metal and its use dates to relatively recent times. However, the unintentional use of nickel is ancient, and can be traced back as far as 3500 BC. Bronzes from what is now Syria had contained up to 2% nickel.[16] Further, there are Chinese manuscripts suggesting that "white copper" (cupronickel, known as baitung) was used there between 1700 and 1400 BC. This Paktong white copper was exported to Britain as early as the 17th century, but the nickel content of this alloy was not discovered until 1822.[17]

In medieval Germany, a red mineral was found in the Erzgebirge (Ore Mountains) which resembled copper ore. However, when miners were unable to extract any copper from it they blamed a mischievous sprite of German mythology, Nickel (similar to Old Nick) for besetting the copper. They called this ore Kupfernickel from the German Kupfer for copper.[18][19][20][21] This ore is now known to be nickeline or niccolite, a nickel arsenide. In 1751, Baron Axel Fredrik Cronstedt was attempting to extract copper from kupfernickel and obtained instead a white metal that he named after the spirit which had given its name to the mineral, nickel.[22] In modern German, Kupfernickel or Kupfer-Nickel designates the alloy cupronickel.

In the United States, the term "nickel" or "nick" was originally applied to the copper-nickel Indian cent coin introduced in 1859. Later, the name designated the three-cent coin introduced in 1865, and the following year the five-cent shield nickel appropriated the designation, which has remained ever since. Coins of pure nickel were first used in 1881 in Switzerland.[19][23]

After its discovery the only source for nickel was the rare Kupfernickel, but from 1824 on the nickel was obtained as byproduct of cobalt blue production. The first large scale producer of nickel was Norway, which exploited nickel rich pyrrhotite from 1848 on. The introduction of nickel in steel production in 1889 increased the demand for nickel and the nickel deposits of New Caledonia, which were discovered in 1865, provided most of the world's supply between 1875 and 1915. The discovery of the large deposits in the Sudbury Basin, Canada in 1883, in Norilsk-Talnakh, Russia in 1920 and in the Merensky Reef, South Africa in 1924 made large-scale production of nickel possible.[17]

Occurrence

Widmanstätten pattern showing the two forms of Nickel-Iron, Kamacite and Taenite, in an octahedrite meteorite

The bulk of the nickel mined comes from two types of ore deposits. The first are laterites where the principal ore minerals are nickeliferous limonite: (Fe, Ni)O(OH) and garnierite (a hydrous nickel silicate): (Ni, Mg)3Si2O5(OH). The second are magmatic sulfide deposits where the principal ore mineral is pentlandite: (Ni, Fe)9S8.

In terms of supply, the Sudbury region of Ontario, Canada, produces about 30% of the world's supply of nickel. The Sudbury Basin deposit is theorized to have been created by a meteorite impact event early in the geologic history of Earth. Russia contains about 40% of the world's known resources at the Norilsk deposit in Siberia. The Russian mining company MMC Norilsk Nickel obtains the nickel and the associated palladium for world distribution. Other major deposits of nickel are found in New Caledonia, France, Australia, Cuba, and Indonesia. Deposits found in tropical areas typically consist of laterites which are produced by the intense weathering of ultramafic igneous rocks and the resulting secondary concentration of nickel bearing oxide and silicate minerals. Recently, a nickel deposit in western Turkey had been exploited, with this location being especially convenient for European smelters, steelmakers and factories. The one locality in the United States where nickel was commercially mined is Riddle, Oregon, where several square miles of nickel-bearing garnierite surface deposits are located. The mine closed in 1987.[24][25] In 2005, Russia was the largest producer of nickel with about one-fifth world share closely followed by Canada, Australia and Indonesia, as reported by the British Geological Survey.

Based on geophysical evidence, most of the nickel on Earth is postulated to be concentrated in the Earth's core. Kamacite and taenite are naturally occurring alloys of iron and nickel. For kamacite the alloy is usually in the proportion of 90:10 to 95:5 although impurities such as cobalt or carbon may be present, while for taenite the nickel content is between 20% and 65%. Kamacite and taenite occur in nickel-iron meteorites.[26]

Extraction and purification

Nickel output in 2005

Nickel is recovered through extractive metallurgy. Most sulfide ores have traditionally been processed using pyrometallurgical techniques to produce a matte for further refining. Recent advances in hydrometallurgy have resulted in recent nickel processing operations being developed using these processes. Most sulfide deposits have traditionally been processed by concentration through a froth flotation process followed by pyrometallurgical extraction.

Nickel is extracted from its ores by conventional roasting and reduction processes which yield a metal of greater than 75% purity. Final purification of nickel oxides is performed via the Mond process, which increases the nickel concentrate to greater than 99.99% purity[27]. This process was patented by L. Mond and was used in South Wales in the 20th century. Nickel is reacted with carbon monoxide at around 50 °C to form volatile nickel carbonyl. Any impurities remain solid while the nickel carbonyl gas passes into a large chamber at high temperatures in which tens of thousands of nickel spheres, called pellets, are constantly stirred. The nickel carbonyl decomposes, depositing pure nickel onto the nickel spheres. Alternatively, the nickel carbonyl may be decomposed in a smaller chamber at 230 °C to create fine nickel powder. The resultant carbon monoxide is re-circulated through the process. The highly pure nickel produced by this process is known as carbonyl nickel. A second common form of refining involves the leaching of the metal matte followed by the electro-winning of the nickel from solution by plating it onto a cathode. In many stainless steel applications, 75% pure nickel can be used without further purification depending on the composition of the impurities.

Nickel sulfide ores undergo flotation (differential flotation if Ni/Fe ratio is too low) and then are smelted. After producing the nickel matte, further processing is done via the Sherritt-Gordon process. First copper is removed by adding hydrogen sulfide, leaving a concentrate of only cobalt and nickel. Solvent extraction then efficiently separates the cobalt and nickel, with the final nickel concentration greater than 99%.

Metal value

The market price of nickel surged throughout 2006 and the early months of 2007; as of April 5, 2007, the metal was trading at 52,300 USD/tonne or 1.47 USD/oz.[28] The price subsequently fell dramatically from these peaks, and as of 19 January 2009 the metal was trading at 10,880 USD/tonne.[28]

The US nickel coin contains 0.04 oz (1.25 g) of nickel, which at the April 2007 price was worth 6.5 cents, along with 3.75 grams of copper worth about 3 cents, making the metal value over 9 cents. Since the face value of a nickel is 5 cents, this made it an attractive target for melting by people wanting to sell the metals at a profit. However, the United States Mint, in anticipation of this practice, implemented new interim rules on December 14, 2006, subject to public comment for 30 days, which criminalize the melting and export of cents and nickels.[29] Violators can be punished with a fine of up to $10,000 and/or imprisoned for a maximum of five years.

As of June 24, 2009 the melt value of a U.S. nickel is $0.0363145 which is less than the face value.[30]

Applications

Nickel superalloy jet engine (RB199) turbine blade

Nickel is used in many industrial and consumer products, including stainless steel, magnets, coinage, rechargeable batteries, electric guitar strings and special alloys. It is also used for plating and as a green tint in glass. Nickel is pre-eminently an alloy metal, and its chief use is in the nickel steels and nickel cast irons, of which there are many varieties. It is also widely used in many other alloys, such as nickel brasses and bronzes, and alloys with copper, chromium, aluminium, lead, cobalt, silver, and gold.[31]

The amounts of nickel used for various applications are 60% used for making nickel steels, 14% used in nickel-copper alloys and nickel silver, 9% used to make malleable nickel, nickel clad, Inconel and other superalloys, 6% used in plating, 3% use for nickel cast irons, 3% in heat and electric resistance alloys, such as Nichrome, 2% used for nickel brasses and bronzes with the remaining 3% of the nickel consumption in all other applications combined.[32][33] In the laboratory, nickel is frequently used as a catalyst for hydrogenation, sometimes Raney nickel, a finely divided form of the metal alloyed with aluminium which adsorbs hydrogen gas. Nickel is often used in coins, or occasionally as a substitute for decorative silver. The American 'nickel' five-cent coin is 75% copper and 25% nickel. The Canadian nickel minted at various periods between 1922-81 was 99.9% nickel, and was magnetic.[34] Various other nations have historically used and still use nickel in their coinage.

Nickel is also used in fire assay as a collector of platinum group elements, as it is capable of full collection of all 6 elements, in addition to partial collection of gold. This is seen through the nature of nickel as a metal, as high throughput nickel mines may run PGE recovery (primarily platinum and palladium), such as Norilsk in Russia and the Sudbury Basin in Canada.

Nickel foam or nickel mesh is used in gas diffusion electrodes for alkaline fuel cells.[35][36]

Biological role

Although not recognized until the 1970s, nickel plays important roles in the biology of microorganisms and plants.[37] In fact urease (an enzyme which assists in the hydrolysis of urea) contains nickel. The NiFe-hydrogenases contain nickel in addition to iron-sulfur clusters. Such [NiFe]-hydrogenases characteristically oxidise H2. A nickel-tetrapyrrole coenzyme, F430, is present in the methyl coenzyme M reductase which powers methanogenic archaea. One of the carbon monoxide dehydrogenase enzymes consists of an Fe-Ni-S cluster.[38] Other nickel-containing enzymes include a class of superoxide dismutase[39] and a glyoxalase.[40]

Toxicity

Exposure to nickel metal and soluble compounds should not exceed 0.05 mg/cm³ in nickel equivalents per 40-hour work week. Nickel sulfide fume and dust is believed to be carcinogenic, and various other nickel compounds may be as well.[41][42] Nickel carbonyl, [Ni(CO)4], is an extremely toxic gas. The toxicity of metal carbonyls is a function of both the toxicity of the metal as well as the carbonyl's ability to give off highly toxic carbon monoxide gas, and this one is no exception. It is explosive in air.[43][44]Sensitized individuals may show an allergy to nickel affecting their skin, also known as dermatitis. Sensitivity to nickel may also be present in patients with pompholyx. Nickel is an important cause of contact allergy, partly due to its use in jewellery intended for pierced ears.[45] Nickel allergies affecting pierced ears are often marked by itchy, red skin. Many earrings are now made nickel-free due to this problem. The amount of nickel which is allowed in products which come into contact with human skin is regulated by the European Union. In 2002 researchers found amounts of nickel being emitted by 1 and 2 Euro coins far in excess of those standards. This is believed to be due to a galvanic reaction.[46]

It was voted Allergen of the Year in 2008 by the American Contact Dermatitis Society.[47]

See also

References

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  2. ^ S. Pfirrmann et al. (2009). "A Dinuclear Nickel(I) Dinitrogen Complex and its Reduction in Single-Electron Steps". Angewandte Chemie International Edition 48: 3357. doi:10.1002/anie.200805862. 
  3. ^ Scerri, Eric R. (2007). The periodic table: its story and its significance. Oxford University Press. pp. 239–240. ISBN 0195305736. http://books.google.com/books?id=SNRdGWCGt1UC&pg=PA239. 
  4. ^ Kittel, Charles (1996). Introduction to Solid State Physics. Wiley. p. 449. ISBN 0471142867. 
  5. ^ National Pollutant Inventory - Nickel and compounds Fact Sheet
  6. ^ UCLA - Magnetostrictive Materials Overview
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  11. ^ Castelvecchi, Davide (2005-04-22). "Atom Smashers Shed Light on Supernovae, Big Bang". http://skyandtelescope.com/news/article_1502_1.asp. Retrieved 2008-11-19. 
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  20. ^ Baldwin, W. H. (1931). "The story of Nickel. II. Nickel comes of age". Journal of Chemical Education 8: 1954. doi:10.1021/ed008p1954. 
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  29. ^ United States Mint Moves to Limit Exportation & Melting of Coins, The United States Mint, press release, December 14, 2006
  30. ^ "United States Circulating Coinage Intrinsic Value Table". Coininflation.com. http://www.coinflation.com/. Retrieved 2009-06-06. 
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  32. ^ Kuck, Peter H.. "Mineral Commodity Summaries 2006: Nickel". United States Geological Survey. http://minerals.usgs.gov/minerals/pubs/commodity/nickel/mcs-2008-nicke.pdf. Retrieved 2008-11-19. 
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  34. ^ "Industrious, enduring–the 5-cent coin". Royal Canadian Mint. 2008. http://www.mint.ca/store/mint/learn/circulation-currency-1100028. Retrieved 2009-01-10. 
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  36. ^ "A New Cathode Design for Alkaline Fuel Cells(AFCs)". Imperial College London. http://perso.ensem.inpl-nancy.fr/Olivier.Lottin/FDFC08/Bidault.pdf. 
  37. ^ Edited by Astrid Sigel, Helmut Sigel, and Roland K. O. Sigel (2008). Astrid Sigel, Helmut Sigel and Roland K. O. Sigel. ed. Nickel and Its Surprising Impact in Nature. Metal Ions in Life Sciences. 2. Wiley. ISBN 978-0-470-01671-8. 
  38. ^ Jaouen, G. (2006). Bioorganometallics: Biomolecules, Labeling, Medicine. Wiley-VCH: Weinheim. ISBN 352730990X. 
  39. ^ Szilagyi, R. K.; Bryngelson, P. A.; Maroney, M. J.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. (2004). "S K-Edge X-ray Absorption Spectroscopic Investigation of the Ni-Containing Superoxide Dismutase Active Site: New Structural Insight into the Mechanism". Journal of the American Chemical Society 126 (10): 3018–3019. doi:10.1021/ja039106v. PMID 15012109. 
  40. ^ Thornalley, P. J. (2003). "Glyoxalase I--structure, function and a critical role in the enzymatic defence against glycation". Biochemical Society Transactions 31 (Pt 6): 1343–1348. doi:10.1042/BST0311343. PMID 14641060. 
  41. ^ Kasprzak; Sunderman Jr, F. W.; Salnikow, K. (2003). "Nickel carcinogenesis.". Mutation research 533 (1-2): 67–97. PMID 14643413. 
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  43. ^ Safety data for nickel carbonyl
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  45. ^ Thyssen J. P., Linneberg A., Menné T., Johansen J. D. (2007). "The epidemiology of contact allergy in the general population—prevalence and main findings". Contact Dermatitis 57 (5): 287–99. doi:10.1111/j.1600-0536.2007.01220.x. PMID 17937743. 
  46. ^ Nestle, O.; Speidel, H.; Speidel, M. O. (2002). "High nickel release from 1- and 2-euro coins". Nature 419: 132. doi:10.1038/419132a. 
  47. ^ "Nickel Named 2008 Contact Allergen of the Year". http://www.nickelallergyinformation.com/2008/06/nickel-named-2008-contact-alle.htm. Retrieved 2009-06-06. 

External links


1911 encyclopedia

Up to date as of January 14, 2010

From LoveToKnow 1911

NICKEL (symbol Ni, atomic weight 58.68 (0 =16)), a metallic element. It has been known from the earliest times, being employed by the Chinese in the form of an alloy called pakfong. It was first isolated in an impure condition in 1751 by A. F. Cronstedt from niccolite, and his results were afterwards confirmed by T. 0. Bergman in 1775 (De niccolo,opusc. 2, p. 231; 3, P. 459; 4, P. 374). It occurs in the uncombined condition and alloyed with iron in meteorites; as sulphide in millerite and nickel blende, as arsenide in niccolite and cloanthite, and frequently in combination with arsenic and antimony in the form of complex sulphides. In recent years it has been found in considerable quantities in New Caledonia in the form of a hydrated silicate of nickel and magnesia approximating to the constitution (NiO, MgO) SiO 2 . nH 2 O (J. Gamier, 1865), and in Canada in the form of nickeliferous pyrrhotines, which consist of sulphides of iron associated with sulphides of nickel and copper, embedded in a matrix of gneiss. At the present time nickel is obtained practically entirely from garnierite and the nickeliferous pyrrhotines. When the former is used it is roasted with calcium sulphate or alkali waste to form a matte which is then blown in a Bessemer converter or heated in a reverberatory furnace with a siliceous flux with the object of forming a rich nickel sulphide. This sulphide is then by further heating converted into the oxide and finally reduced to the state of metal by ignition with carbon in clay crucibles. The process adopted for the Canadian ores, which are poor in copper and nickel, consists in a preliminary roasting in heaps and smelting in a blast furnace in order to obtain a matte, which is then further smelted with a siliceous flux for a rich matte. This rich matte is then mixed with coke and salt-cake and melted down in an open hearth furnace. The nickel sulphide so obtained is then roasted to oxide and reduced to metal. For a wet method of extraction of the matte see Christofle and Bouilhet, French Patent 111591 (1876). L. Mond (Jour. Soc. Chem. Ind. 18 95, p. 945) has obtained metallic nickel from the Canadian mattes by first roasting them and then eliminating copper by the action of sulphuric acid, the product so obtained being then exposed to the reducing action of producer gas at about 350° C. The reduced metal is then passed into a "volatilizer" and exposed to the action of carbon monoxide at about 80° C., the nickel carbonyl so formed being received in a chamber heated to 180-200° C., where it decomposes, the nickel being deposited and the carbon monoxide returned to the volatilizer. For an electrolytic method of treating mattes, see T. Ulke, Moniteur scient., 18 97, 49, p. 45 0. The metal as obtained by industrial methods rarely contains more than about 99-99.5% of nickel, the chief impurities being copper, iron, cobalt, silicon and carbon.

Production

(lb). w

Export

(lb).

Production

(lb).

Export

(lb).

1900

7,080,227

1 3,493, 2 39

1905

18,876,315

11,970,557

1901

9, 1 89,047

9,537,55 8

1906

21 ,49 0 ,955

20,653,845

1902

10,693,410

3,883,264

1907

21,189,793

19,376,335

1903

12,505,510

9, 0 3 2 ,554

1908

19,143,111

19,419,893

1904

10 ,547, 88 3

14,229,973

The following tables show the output of nickel from Canada and the shipments of nickel ore from New Caledonia in recent years: Canada New Caledonia (See Rothwell's Mineral Industry (1908), pp.

The metal may also be obtained on the small scale by the reduction of the oxide by hydrogen or by carbon,, by ignition of the oxalate or of nickel ammonium oxalate (J. J. Berzelius), by reduction of the chloride in a current of hydrogen (E. Peligot), by electrolysis of nickel ammonium sulphate (Winkler, Zeit. anorg. Chem. 1894, 8, p. 1), and by reduction of the chloride with calcium carbide.

It is a greyish white metal, and is very malleable and ductile. Its specific gravity varies according to the method employed for its preparation, the extreme values being 8.279 and 9.25. It melts between 1400-1600° C. Its specific heat increases with rise of temperature, the mean value from 15° to 100° C. being 0.1084 (A. Naccari, Ganz., 1888, 18, p. 13). It is magnetic, but loses its magnetism when heated, the loss being complete at about 34 0 -35 0 ° C. On the physical constants see H. Copaux, Comptes rendus, 1905, 140, p. 651. Nickel occludes hydrogen readily, is attacked by the halogen elements, and oxidizes easily when heated in air. In the massive state it is unacted upon by dry air, but if moistened with acidified water, oxidation takes place slowly. When obtained by reduction processes at as low a temperature as possible the finely divided metal so formed is pyrophoric, and according to P. Schutzenberger (Comptes rendus, 1891,113, p. 177) dry hydrochloric acid gas converts this form into nickel chloride and a volatile compound of composition NiHC1. It decomposes water at a red heat. According to E. St Edme (Comptes rendus, 1886, 106, p. 1079) sheet nickel is passive to nitric acid, and the metal remains passive even when heated to redness in a current of hydrogen. On the reduction of organic compounds by hydrogen in ,the presence of metallic nickel see P. Sabatier and J. B. Senderens, Ann. Chim. Phys., 1905 [8], 4, pp. 3 1 9, 433.

It rapidly oxidizes when fused with caustic soda, but is scarcely acted upon by caustic potash (W. Dittmar, Jour. Soc. Chem. Ind., 1884, 3, p. 103). Hydrochloric and sulphuric acids are almost without action on the metal, but it dissolves readily in dilute nitric acid. Nickel salts are antiseptic; they arrest fermentation and stop the growth of plants. Nickel carbonyl, however, is extremely poisonous. On the toxic properties of nickel salts see A. Riche and Laborde, Jour. Pharm. Chem., 1888, [51, 1 7, pp. I, 59, 97.

Nickel is used for the manufacture of domestic utensils, for crucibles, coinage, plating, and for the preparation of various alloys, such as German silver, nickel steels such as invar (nickel, 35.7%; steel, 64.3%), which has a negligible coefficient of thermal expansion, and constantan (nickel, 45%; copper, 55%), which has a negligible thermal coefficient of its electrical resistance.

Compounds. Nickel Oxides. Several oxides of nickel are known. A suboxide, Ni 2 O (?), described by W. Muller (Pogg. Ann., 1869, 212, p. 59), is not certainly known. The monoxide, NiO, occurs naturally as bunsenite, and is obtained artificially when nickel hydroxide, carbonate, nitrate or sulphate is heated. It may also be prepared by the action of nickel on water, by the reduction of the oxide N1203 with hydrogen at about 200° C. (H. Moissan, Ann. Chim. Phys., [5], 21, p. 199), or by heating nickel chloride with sodium carbonate and extracting the fused mass with water. It is a green powder which becomes yellow when heated. It dissociates at a red heat, and is readily reduced to the metal when heated with carbon or in a current of hydrogen. It is readily soluble in acids, forming salts, the rate of solution being rapid if the oxide is in the amorphous condition, but slow if the oxide is crystalline. The hydroxide, Ni(OH) 2, is obtained in the form of a greenish amorphous powder when nickel salts are precipitated by the caustic alkalis. It is readily soluble in acids and in an aqueous solution of ammonia. Nickel sesquioxide, N1203, is formed when the nitrate is decomposed by heat at the lowest possible temperature, by a similar decomposition of the chlorate, or by fusing the chloride with potassium chlorate. It is a black powder, the composition of which is never quite definite, but approximates to the formula given above. When heated with oxy-acids it dissolves, with evolution of oxygen, and with hydrochloric acid it evolves chlorine. Numerous hydrated forms of the oxide have been de- scribed (see W. Wernicke, Pogg. Ann., 1870, 217, p. 122). A peroxide, N102, has been obtained in the form of dinickelite of barium, BaO. 2N102, by heating the monoxide with anhydrous baryta in the electric furnace (E. Dufau, Comptes rendus, 1896, 123, P. 495). G. Pellini and D. Meneghini (Zeit. anorg. Chem., 1908, 60, p. 178) obtained a greyish green powder of composition N102. xH20, by adding an alcoholic solution of potassium hydrate to nickelchloride and hydrogen peroxide at -50°. It has all the reactions of hydrogen peroxide, and S. Tanatar (Ber., 1909, 42, p. 1516) regards it as N104-1 2 O 2. An oxide, Ni 3 0 4, has been obtained by heating nickel chloride in a current of moist oxygen at about 400° C. (H. Baubigny, Comptes rendus, 1878, 87, p. 1082), or by heating the sesquioxide in hydrogen at 190° C. (H. Moissan, Ann. Chico. Phys., 1890 [5], 21, p. 199). The former method yields greyish, metallic-looking, microscopic crystals, the latter a grey amorphous powder. A hydrated form, Ni 3 0 4 ..2H 2 O, is obtained when the monoxide is fused with sodium peroxide at a red heat and the fused mass extracted with water.

1900.

1901.

1902.

1903.

1904.

1905.

1906.

1907.

1908.

Metric tons .

100,319

133,676

12 9, 6 53

77,360

98,665

125,289

130,688

101,708

120,028

Nickel Salts.-Only one series of salts is known, namely those corresponding to the monoxide. In the anhydrous state they are usually of a yellow colour, whilst in the hydrated condition they are green. They may be recognized by the brownish violet colour they impart to a borax bead when heated in an oxidizing flame. The caustic alkalis added to solutions of nickel salts give a pale green precipitate of the hydroxide, insoluble in excess of the precipitant. This latter reaction is hindered by the presence of many organic acids (tartaric acid, citric acid, &c.). Potassium cyanide gives a greenish yellow precipitate of nickel cyanide, Ni(CN) 2, soluble in excess of potassium cyanide, forming a double salt, Ni(CN)2.2KCN, which remains unaltered when boiled with excess of potassium cyanide in presence of air (cf. Cobalt). Ammonium sulphide precipitates black nickel sulphide, which is somewhat soluble in excess of the precipitate (especially if yellow ammonium sulphide be used), forming a dark-coloured solution. Ammonium hydroxide gives a green precipitate of the hydroxide, soluble in excess of ammonia, forming a blue solution. Numerous methods have been devised for the separation of nickel and cobalt, the more important of which are: -the cobaltinitrite method by which the cobalt is precipitated in the presence of acetic acid by means of potassium nitrite (the alkaline earth metals must not be present); the cyanide method (J. v. Liebig, Ann., 1848, 6 5, p. 2 44; 1853, 87, p.128), in which the two metals are precipitated by excess of potassium cyanide in alkaline solution, bromine being afterwards added and the solution warmed, when the nickel is precipitated. The latter method has been modified by adding potassium cyanide in slight excess to the solution of the mixed salts, heating for some time and then adding mercuric oxide and water, the whole being then warmed on the water bath, when a precipitate of mercuric oxide and nickel hydroxide is obtained 666, 670).

(Liebig). M. Ilinski and G. v. Knorre (Ber., 1885, 18, p. 169) separate the metals by adding nitros01 3-naphthol in the presence of 50% acetic acid, a precipitate of cobalti nitroso-13-naphthol, [C 10 H 6 0(NO)] 3 Co, insoluble in hydrochloric acid, being formed, whilst the corresponding nickel compound dissolves in hydrochloric acid. E. Pinerua separates the metals by taking advantage of the fact that cobalt chloride is soluble in ether which has been saturated with hydrochloric acid gas at low temperature. For an examination of the above and other methods see E. Hintz, Zeit. anal. Chem., 1891, 30, p. 227. Nickel fluoride, NiF 2, obtained by the action of hydrofluoric acid on nickel chloride, crystallizes in yellowish green prisms which volatilise above m000° C. It is difficultly soluble in water, and combines with the alkaline fluorides to form double salts. Nickel chloride, NiC1 2, is obtained in the anhydrous condition by heating the hydrated salt to 140° C., or by gently heating the finely divided metal in a current of chlorine. It readily sublimes when heated in a current of chlorine, forming golden yellow scales. It is easily reduced when heated in hydrogen. It forms crystalline compounds with ammonia and the organic bases. It is soluble in alcohol and in water. Three hydrated forms are known, viz. a mono-, di-, and hexa-hydrate; the latter being the form usually obtained by the solution of the oxide or carbonate in hydrochloric acid. Nickel chloride ammonia, NiC1 2.6NH3, is obtained as a white powder when anhydrous nickel chloride is exposed to the action of ammonia gas (H. Rose, Pogg. Ann., 1830, 96, p. 155), or in the form of blue octahedra by evaporating a solution of nickel chloride in aqueous ammonia. When heated to 100° C. it loses four molecules of ammonia. Two hydrated forms have been described, one containing three molecules of water and the other half a molecule. Numerous double chlorides of nickel and other metals are known. The bromide and iodide of nickel resemble the chloride and are prepared in a similar fashion.

Several sulphides of the element have been obtained. A subsulphide, Ni 2 S(?), results when the sulphate is heated with sulphur or when the precipitated monosulphide is heated in a current of hydrogen. It forms a light yellow amorphous mass which is almost insoluble in acids. The monosulphide, NiS, is obtained by heating nickel with sulphur, by heating the monoxide with sulphuretted hydrogen to a red heat, and by heating potassium sulphide with nickel chloride to 160-180° C. When prepared by dry methods it is an exceedingly stable, yellowish, somewhat crystalline mass. When prepared by the precipitation of nickel salts with alkaline sulphide in neutral solution it is a greyish black amorphous compound which readily oxidizes in moist air, forming a basic nickel sulphate. The freshly precipitated sulphide is soluble in sulphurous acid and somewhat soluble in hydrochloric acid and yellow ammonium sulphide (see H. Baubigny, Comptes rendus, 1882, 94, pp. 961, 1183; 95, P. 34). Nickel sulphate, NiSO 4, is obtained anhydrous as a yellow powder when any of its hydrates are heated. When heated with carbon it is reduced to the metal. It forms hydrates containing one, two, five, six and seven molecules of water. The heptahydrate is obtained by dissolving the metal or its oxide, hydroxide or carbonate in dilute sulphuric acid (preferably in the presence of a small quantity of nitric acid), and allowing the solution to crystallize between 15° and 20° C. It crystallizes in emerald-green rhombic prisms and is moderately soluble in water. It effloresces gradually on exposure to air and passes into the hexahydrate. It loses four molecules of water of crystallization when heated to 100° C. and becomes anhydrous at about 300° C. The hexahydrate is dimorphous, a tetragonal form being obtained by crystallization of a solution of the heptahydrate between 20° and 30° C., and a monoclinic form between 50° and 70° C. Nickel sulphate combines with many metallic sulphates to form double salts, and also forms addition compounds with ammonia aniline and hydroxylamine. The nitrate, Ni(NO 3) 2.6H 2 O, is obtained by dissolving the metal in dilute nitric acid and concentrating the solution between 40° and 50° C. It crystallizes in green prisms which deliquesce rapidly on exposure to moist air.

Nickel carbonyl, Ni(CO) 4, is obtained as a colourless mobile liquid by passing carbon monoxide over reduced nickel at a temperature of about 60° C. (L. Mond, Langer and Quincke, Jour. Chem. Soc., 18 9 0, 57, P 749). It boils at 43° C. (751 mm.), and sets at -25° C. to a mass of crystalline needles. It is readily soluble in hydrocarbon solvents, in chloroform and in alcohol. Its critical pressure is 30 atmospheres and its critical temperature is in the neighbourhood of 195° C. (J. Dewar, Proc. Roy. Soc., 1903, 71, p. 427). It decomposes with explosive violence when heated rapidly. Dewar and Jones (Journ. Chem. Soc., 1904, p. 203) have made an exhaustive study of its reactions, and find that it is decomposed by the halogens (dissolved in carbon tetrachloride) with liberation of carbon monoxide and formation of a nickel halide. Cyanogen iodide and iodine monoand tri-chloride effect similar decompositions with simultaneous liberation of iodine; sulphuric acid reacts slowly, forming nickel sulphate and liberating hydrogen and carbon monoxide. Hydrochloric and hydrobromic acids are without action; hydriodic acid only reacts slowly. With aromatic hydrocarbons in the presence of anhydrous aluminium chloride, in the cold, there is a large evolution of hydrochloric acid gas, and an aldehyde is formed; at 100° C., on the other hand, anthracene derivatives are produced. Thus by using benzene, benzaldehyde and anthracene are obtained. Dewar and Jones suggest that in the latter reaction it is the metallic nickel which is probably the reducing agent effecting the change, since it is only dissolved in any quantity when the anthracene hydrocarbon is produced. When mesitylene is used, the reaction does not proceed beyond the aldehyde stage since hydrocarbon formation is prevented by the presence of a methyl group in the ortho-position to the -CHO group. Acids and alkalis are in general without action on nickel carbonyl. The vapour of nickel carbonyl burns with a luminous flame, a cold surface depressed in the flame being covered with a black deposit of nickel. It is an extremely powerful poison. Mond and his assistants have discovered several other carbonyls. For example cobalt gives Co(CO) 4, as orange crystals which melt at 51°, decomposing at a higher temperature, giving Co(C0) 3 and CO at 60°; Co(C0) 3 forms jet black crystals. For iron carbonyls see Iron; also L. Mond, H. Hirtz and M. D. Cowap, Jour. Chem. Soc., 1910, 97, p. 798. Nickel carbonate, NiC03, is obtained in the anhydrous state by heating nickel chloride with calcium carbonate in a sealed tube to 150°C. (H. de Senarmont, Ann. Claim. Phys., 1850 [3], 30, 138). It crystallizes in microscopic rhombohedra insoluble in cold acids. By precipitation of nickel salts with solutions of the alkaline carbonates, basic carbonates of variable composition are obtained.

Numerous determinations of the atomic weight of nickel have been published, the values obtained varying from 58 o to approximately 59.5 The more recent work of T. W. Richards and Cushman (Chem. News, 18 99, 79, 163, 174, 185) gives for the atomic weight of the metal the values 58.69 and 58.70.


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Wiktionary

Up to date as of January 15, 2010

Definition from Wiktionary, a free dictionary

See also nickel

Contents

German

Chemical element
Ni Previous: Cobalt (Co)
Next: Kupfer (Cu)

Pronunciation

  • IPA: /ˈnɪkl̩/, /ˈnɪkəl/

Noun

Nickel n.

  1. nickel (a silvery elemental metal with an atomic number of 28 and symbol Ni).

Related terms

  • vernickeln

Simple English

File:Nickel
A chunk of nickel metal

Nickel (chemical symbol Ni) is a chemical element. It has an atomic number of 28 and an atomic mass of about 59. It has 28 protons. It is a transition metal.

Contents

Properties

Physical properties

Nickel is a silver-white metal. It is a little golden colored. It is easily polished (made shiny). It is magnetic. It is not magnetic when heated above

  1. REDIRECT Template:Convert/°C. It is not soft like many other metals. It can be stretched into wires easily. It is not radioactive.

Chemical properties

Nickel is not a reactive metal. It dissolves slowly in acids. It does not rust like iron. It makes a thin coating of nickel(II) oxide which stops more corrosion. Aluminium does a similar thing.

Chemical compounds

Nickel is in several oxidation states. +2 [Nickel(II)]is the most common. +3 [Nickel(III)] also is common. Nickel in its +2 oxidation state is green. Nickel(II) chloride is a common +2 oxidation state compound. Nickel(II) oxide is normally dark green, but sometimes it is gray. This is because some of the nickel is in the +3 oxidation state (nickel(III). Nickel(III) compounds are oxidizing agents. They also are grayish. Nickel compounds can be green, blue, gray, or black.

Occurrence

[[File:|thumb|Limonite, a common nickel ore]] Nickel is not normally found as a metal in the ground. Sometimes meteorites have nickel and iron metal in them. Normally nickel is in minerals. Nickel hydroxides, sulfides, and silicates are common ores. Russia makes the most nickel.

History

Nickel was found when a copper-colored ore did not make copper metal. Later it was found out that the ore was actually a nickel ore. Nickel was isolated as a metal in 1751. At first, the copper colored nickel ore was the only source. Later, it was made as a byproduct of cobalt blue making.

Preparation

Nickel is made from sulfide ores. They are heated to melt them and concentrate them. They are also separated by oils. Nickel is made from its sulfide by heating it in air. This oxidizes the sulfide to sulfur dioxide, leaving liquid nickel behind. This nickel is not pure. Only about 75% of it is nickel.

Nickel can be made purer. It can react with carbon monoxide to make nickel carbonyl, a gas when warm. All the impurities are left behind. The nickel carbonyl is blown into nickel pellets, where it coats the pellets with pure nickel and puts out carbon monoxide. The carbon monoxide is reused (used again).

Another way to make the nickel pure is by dissolving it in an acid. Then it is electrolyzed to make nickel at the cathode.

Uses

As a metal

Nickel is used in metal alloys. Stainless steel contains nickel. Nickel is also used in nichrome, a name for a nickel-chromium alloy. Nickel is used in coins such as nickels. It is used in magnets. Nickel is used in special expensive alloys called superalloys.

As chemical compounds

It is used in rechargeable batteries. They are also used to electroplate nickel on items. Nickel and some of its compounds are also used as a catalyst.

Safety

Nickel can irritate skin. That is why nickel jewelry is bad for some people. Some nickel salts are carcinogens. Nickel is not as toxic as other metals such as lead or mercury but it is still toxic.

See also








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