Nickeline or niccolite is a
mineral
In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. ( ...
consisting primarily of
nickel
Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
arsenide
In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
(NiAs). The naturally-occurring mineral contains roughly 43.9% nickel and 56.1% arsenic by mass, but composition of the mineral may vary slightly.
[
Small quantities of ]sulfur
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, iron
Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
and cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
are usually present, and sometimes the arsenic is largely replaced by antimony
Antimony is a chemical element with the symbol Sb (from la, stibium) and atomic number 51. A lustrous gray metalloid, it is found in nature mainly as the sulfide mineral stibnite (Sb2S3). Antimony compounds have been known since ancient t ...
. This last forms an isomorphous series with breithauptite
Breithauptite is a nickel antimonide mineral with the simple formula NiSb. Breithauptite is a metallic opaque copper-red mineral crystallizing in the hexagonal - dihexagonal dipyramidal crystal system. It is typically massive to reniform in habit, ...
(nickel antimonide).
Etymology and history
Medieval miners looking for copper in the German Erzgebirge ("Ore Mountains") would sometimes find a red mineral, superficially resembling copper ore. Upon attempting extraction, no copper was produced, and subsequently, the miners would be afflicted with mysterious illness. They blamed a mischievous sprite of German mythology, Nickel (similar to ''Old Nick'') for besetting the copper (German: Kupfer). This German equivalent of "copper-nickel" was used as early as 1694 (other old German synonyms are ''Rotnickelkies'' and ''Arsennickel'').
In 1751, Baron Axel Fredrik Cronstedt
Baron Axel Fredrik Cronstedt (''/kroonstet/'' 23 December 1722 – 19 August 1765) was a Swedish mineralogist and chemist who discovered the element nickel in 1751 as a mining expert with the Bureau of Mines.
Cronstedt is considered a founder ...
was attempting to extract copper from kupfernickel mineral, and obtained instead a white metal which he named "nickel", after the sprite. In modern German, Kupfernickel and Kupfer-Nickel designates the alloy Cupronickel
Cupronickel or copper-nickel (CuNi) is an alloy of copper that contains nickel and strengthening elements, such as iron and manganese. The copper content typically varies from 60 to 90 percent. (Monel is a nickel-copper alloy that contains a minimu ...
.
The names subsequently given to the ore, ''nickeline'' from F. S. Beudant, 1832, and ''niccolite,'' from J. D. Dana, 1868, refer to the presence of nickel
Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
; in Latin, ''niccolum.''
In 1971, the International Mineralogical Association recommended use of the name nickeline rather than niccolite.
Preparation of NiAs
The main compound within nickeline, nickel arsenide (NiAs), can be prepared by direct combination of the elements:
Occurrence
Nickeline is formed by hydrothermal modification of ultramafic rocks and associated ore deposits
Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 April ...
, and may be formed by replacement of nickel-copper bearing sulfides (replacing pentlandite
Pentlandite is an iron–nickel sulfide with the chemical formula . Pentlandite has a narrow variation range in Ni:Fe but it is usually described as having a Ni:Fe of 1:1. It also contains minor cobalt, usually at low levels as a fraction of wei ...
, and in association with copper arsenic sulfides), or via metasomatism
Metasomatism (from the Greek μετά ''metá'' "change" and σῶμα ''sôma'' "body") is the chemical alteration of a rock by hydrothermal and other fluids. It is the replacement of one rock by another of different mineralogical and chemical co ...
of sulfide-free ultramafic rocks, where metasomatic fluids introduce sulfur, carbonate, and arsenic. This typically results in mineral assemblaged including millerite
Millerite is a nickel sulfide mineral, Ni S. It is brassy in colour and has an acicular habit, often forming radiating masses and furry aggregates. It can be distinguished from pentlandite by crystal habit, its duller colour, and general la ...
, heazelwoodite and metamorphic pentlandite
Pentlandite is an iron–nickel sulfide with the chemical formula . Pentlandite has a narrow variation range in Ni:Fe but it is usually described as having a Ni:Fe of 1:1. It also contains minor cobalt, usually at low levels as a fraction of wei ...
-pyrite
The mineral pyrite (), or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula Iron, FeSulfur, S2 (iron (II) disulfide). Pyrite is the most abundant sulfide mineral.
Pyrite's metallic Luster (mineralogy), lust ...
via sulfidation and associated arsenopyrite-nickeline-breithauptite.
Associated minerals include: arsenopyrite
Arsenopyrite ( IMA symbol: Apy) is an iron arsenic sulfide (FeAsS). It is a hard ( Mohs 5.5-6) metallic, opaque, steel grey to silver white mineral with a relatively high specific gravity of 6.1. When dissolved in nitric acid, it releases elem ...
, barite, silver
Silver is a chemical element with the Symbol (chemistry), symbol Ag (from the Latin ', derived from the Proto-Indo-European wikt:Reconstruction:Proto-Indo-European/h₂erǵ-, ''h₂erǵ'': "shiny" or "white") and atomic number 47. A soft, whi ...
, cobaltite
Cobaltite is a sulfide mineral composed of cobalt, arsenic, and sulfur, Co As S. Its impurities may contain up to 10% iron and variable amounts of nickel.Klein, Cornelus and Cornrlius Hurlbut, 1996, ''Manual of Mineralogy'', 20th ed., Wiley, p. ...
, pyrrhotite
Pyrrhotite is an iron sulfide mineral with the formula Fe(1-x)S (x = 0 to 0.2). It is a nonstoichiometric variant of FeS, the mineral known as troilite.
Pyrrhotite is also called magnetic pyrite, because the color is similar to pyrite and it i ...
, pentlandite
Pentlandite is an iron–nickel sulfide with the chemical formula . Pentlandite has a narrow variation range in Ni:Fe but it is usually described as having a Ni:Fe of 1:1. It also contains minor cobalt, usually at low levels as a fraction of wei ...
, chalcopyrite
Chalcopyrite ( ) is a copper iron sulfide mineral and the most abundant copper ore mineral. It has the chemical formula CuFeS2 and crystallizes in the tetragonal system. It has a brassy to golden yellow color and a hardness of 3.5 to 4 on the Mo ...
, breithauptite
Breithauptite is a nickel antimonide mineral with the simple formula NiSb. Breithauptite is a metallic opaque copper-red mineral crystallizing in the hexagonal - dihexagonal dipyramidal crystal system. It is typically massive to reniform in habit, ...
and maucherite
Maucherite is a grey to reddish silver white nickel arsenide mineral. It crystallizes in the tetragonal crystal system. It occurs in hydrothermal veins alongside other nickel arsenide and sulfide minerals. It is metallic and opaque with a hardne ...
. Nickeline alters to annabergite
Annabergite is an arsenate mineral consisting of a hydrous nickel
arsenate, Ni3(AsO4)2·8H2O, crystallizing in the monoclinic system and isomorphous with vivianite and erythrite. Crystals are minute and capillary and rarely met with, the mineral ...
(a coating of green nickel arsenate) on exposure to moist air.
Most of these minerals can be found in the areas surrounding Sudbury and Cobalt
Cobalt is a chemical element with the symbol Co and atomic number 27. As with nickel, cobalt is found in the Earth's crust only in a chemically combined form, save for small deposits found in alloys of natural meteoric iron. The free element, pr ...
, Ontario
Ontario ( ; ) is one of the thirteen provinces and territories of Canada.Ontario is located in the geographic eastern half of Canada, but it has historically and politically been considered to be part of Central Canada. Located in Central Ca ...
. Other localities include the eastern flank of the Widgiemooltha Dome, Western Australia, from altered pentlndite-pyrite-pyrrhotite assemblages within the Mariners, Redross and Miitel nickel mines where nickeline is produced by regional Au-As-Ag-bearing alteration and carbonate metasomatism. Other occurrences include within similarly modified nickel mines of the Kambalda
Kambalda is a small mining town about from the mining city of Kalgoorlie in Western Australia, within the Goldfields. It is split into two townsites apart, Kambalda East and Kambalda West; and is located on the western edge of a giant salt ...
area.
Crystal structure
The unit cell
In geometry, biology, mineralogy and solid state physics, a unit cell is a repeating unit formed by the vectors spanning the points of a lattice. Despite its suggestive name, the unit cell (unlike a unit vector, for example) does not necessaril ...
of nickeline is used as the prototype of a group of crystalline solids with similar crystal structures. The structure consists of two interpenetrating sublattices: a primitive hexagonal nickel sublattice and a hexagonal close-packed
In geometry, close-packing of equal spheres is a dense arrangement of congruent spheres in an infinite, regular arrangement (or lattice). Carl Friedrich Gauss proved that the highest average density – that is, the greatest fraction of space occu ...
arsenic sublattice. Each nickel atom is octahedrally coordinated to six arsenic atoms, while each arsenic atom is trigonal prismatically coordinated to six nickel atoms.[Inorganic Chemistry by Duward Shriver and Peter Atkins, 3rd Edition, W.H. Freeman and Company, 1999, pp.47,48.] Compounds adopting the NiAs structure are generally the chalcogen
The chalcogens (ore forming) ( ) are the chemical elements in group 16 of the periodic table. This group is also known as the oxygen family. Group 16 consists of the elements oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and the radioac ...
ides, arsenide
In chemistry, an arsenide is a compound of arsenic with a less electronegative element or elements. Many metals form binary compounds containing arsenic, and these are called arsenides. They exist with many stoichiometries, and in this respect a ...
s, antimonides Antimonides (sometimes called stibnides) are compounds of antimony with more electropositive elements. The antimonide ion is Sb3−.
Reduction of antimony by alkali metals or by other methods leads to alkali metal antimonides of various types. Kn ...
and bismuth
Bismuth is a chemical element with the Symbol (chemistry), symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental ...
ides of transition metal
In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
s.
The following are the members of the nickeline group:[
* Achavalite:
*]Breithauptite
Breithauptite is a nickel antimonide mineral with the simple formula NiSb. Breithauptite is a metallic opaque copper-red mineral crystallizing in the hexagonal - dihexagonal dipyramidal crystal system. It is typically massive to reniform in habit, ...
:
*Freboldite:
*Kotulskite:
*Langistite:
*Nickeline:
*Sobolevskite:
*Sudburyite:
Economic importance
Nickeline is rarely used as a source of nickel due to the presence of arsenic, which is deleterious to most smelting
Smelting is a process of applying heat to ore, to extract a base metal. It is a form of extractive metallurgy. It is used to extract many metals from their ores, including silver, iron, copper, and other base metals. Smelting uses heat and a ...
and milling techniques. When nickel sulfide ore deposits have been altered to produce nickeline, often the presence of arsenic renders the ore uneconomic when concentrations of As reach several hundred parts per million. However, arsenic bearing nickel ore may be treated by blending with 'clean' ore sources, to produce a blended feedstock which the mill and smelter can handle with acceptable recovery.
The primary problem for treating nickeline in conventionally constructed nickel mills is the specific gravity of nickeline versus that of pentlandite. This renders the ore difficult to treat via the froth flotation technique. Within the smelter itself, the nickeline contributes to high arsenic contents which require additional reagents and fluxes to strip from the nickel metal.
References
*Dana's Manual of Mineralogy {{ISBN, 0-471-03288-3
Nickel minerals
Arsenide minerals
Hexagonal minerals
Minerals in space group 194