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Pyrite
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Pyrite cubic crystals on marl from Navajún, La Rioja, Spain (size: 95 by 78 millimetres (3.7 by 3.1 in), 512 grams (18.1 oz); main crystal: 31 millimetres (1.2 in) on edge)
General
Category Sulfide mineral
Formula
(repeating unit)
FeS2
Strunz classification 02.EB.05a
Dana classification 2.12.1.1
Crystal symmetry Isometric diploidal
Space group: PaTemplate:Overline
H-M symbol: 2/mTemplate:Overline
Unit cell a = 5.417 Å, Z=4
Identification
Formula mass 119.98 g/mol
Color Pale brass-yellow reflective; tarnishes darker and iridescent
Crystal habit Cubic, faces may be striated, but also frequently octahedral and pyritohedron. Often inter-grown, massive, radiated, granular, globular, and stalactitic.
Crystal system Isometric
Twinning Penetration and contact twinning
Cleavage Indistinct on {001}; partings on {011} and {111}
Fracture Very uneven, sometimes conchoidal
Tenacity Brittle
Mohs scale hardness 6–6.5
Luster Metallic, glistening
Streak Greenish-black to brownish-black
Diaphaneity Opaque
Specific gravity 4.95–5.10
Density 4.8–5 g/cm3
Fusibility 2.5–3 to a magnetic globule
Solubility Insoluble in water
Other characteristics paramagnetic
References [1][2][3][4]

The mineral pyrite, or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula FeS2. This mineral's metallic luster and pale brass-yellow hue give it a superficial resemblance to gold, hence the well-known nickname of fool's gold. The color has also led to the nicknames brass, brazzle, and Brazil, primarily used to refer to pyrite found in coal.[5][6]

Pyrite is the most common of the sulfide minerals. The name pyrite is derived from the Greek πυρίτης (pyritēs), "of fire" or "in fire",[7] in turn from πύρ (pyr), "fire".[8] In ancient Roman times, this name was applied to several types of stone that would create sparks when struck against steel; Pliny the Elder described one of them as being brassy, almost certainly a reference to what we now call pyrite.[9] By Georgius Agricola's time, ca. 1550, the term had become a generic term for all of the sulfide minerals.[10]

Pyrite is usually found associated with other sulfides or oxides in quartz veins, sedimentary rock, and metamorphic rock, as well as in coal beds and as a replacement mineral in fossils. Despite being nicknamed fool's gold, pyrite is sometimes found in association with small quantities of gold. Gold and arsenic occur as a coupled substitution in the pyrite structure. In the Carlin–type gold deposits, arsenian pyrite contains up to 0.37 wt% gold.[11]

UsesEdit

File:Pyrite from Ampliación a Victoria Mine, Navajún, La Rioja, Spain 2.jpg

Pyrite enjoyed brief popularity in the 16th and 17th centuries as a source of ignition in early firearms, most notably the wheellock, where the cock held a lump of pyrite against a circular file to strike the sparks needed to fire the gun.Script error

Pyrite has been used since classical times to manufacture copperas, that is, iron(II) sulfate. Iron pyrite was heaped up and allowed to weather (an example of an early form of heap leaching). The acidic runoff from the heap was then boiled with iron to produce iron sulfate. In the 15th century, such leaching began to replace the burning of sulfur as a source of sulfuric acid. By the 19th century, it had become the dominant method.[1]

Pyrite remains in commercial use for the production of sulfur dioxide, for use in such applications as the paper industry, and in the manufacture of sulfuric acid. Thermal decomposition of pyrite into FeS (iron(II) sulfide) and elemental sulfur starts at 550 °C; at around 700 °C pS2 is about 1 atm.[2]

A newer commercial use for pyrite is as the cathode material in Energizer brand non-rechargeable lithium batteries.[3]

Pyrite is a semiconductor material with a band gap of 0.95 eV.[4]

During the early years of the 20th century, pyrite was used as a mineral detector in radio receivers, and is still used by 'crystal radio' hobbyists. Until the vacuum tube matured, the crystal detector was the most sensitive and dependable detector available – with considerable variation between mineral types and even individual samples within a particular type of mineral. Pyrite detectors occupied a midway point between galena detectors and the more mechanically complicated perikon mineral pairs. Pyrite detectors can be as sensitive as a modern 1N34A germanium diode detector.[5][6]

Pyrite has been proposed as an abundant, inexpensive material in low cost photovoltaic solar panels.[7] Synthetic iron sulfide was used with copper sulfide to create the photovoltaic material.[8]

Pyrite is used to make marcasite jewelry. Marcasite jewelry, made from small faceted pieces of pyrite, often set in silver, was known since ancient times and was popular in the Victorian era.[9] At the time when the term became common in jewelry making, "marcasite" referred to all iron sulfides including pyrite, and not to the orthorhombic FeS2 mineral marcasite which is lighter in color, brittle and chemically unstable, and thus not suitable for jewelry making. Marcasite jewelry does not actually contain the mineral marcasite.

Formal oxidation states for pyrite, marcasite, and arsenopyriteEdit

From the perspective of classical inorganic chemistry, which assigns formal oxidation states to each atom, pyrite is probably best described as Fe2+S22−. This formalism recognizes that the sulfur atoms in pyrite occur in pairs with clear S–S bonds. These persulfide units can be viewed as derived from hydrogen disulfide, H2S2. Thus pyrite would be more descriptively called iron persulfide, not iron disulfide. In contrast, molybdenite, Template:MolybdenumS2, features isolated sulfide (S2−) centers and the oxidation state of molybdenum is Mo4+. The mineral arsenopyrite has the formula FeAsS. Whereas pyrite has S2 subunits, arsenopyrite has [AsS] units, formally derived from deprotonation of H2AsSH. Analysis of classical oxidation states would recommend the description of arsenopyrite as Fe3+[AsS]3−.[10]

CrystallographyEdit

File:FeS2structure.png

Iron-pyrite FeS2 represents the prototype compound of the crystallographic pyrite structure. The structure is simple cubic and was among the first crystal structures solved by X-ray diffraction.[11] It belongs to the crystallographic space group PaTemplate:Overline and is denoted by the Strukturbericht notation C2. Under thermodynamic standard conditions the lattice constant a of stoichiometric iron pyrite FeS2 amounts to 541.87 pm.[12] The unit cell is composed of a Fe face-centered cubic sublattice into which the S ions are embedded. The pyrite structure is also used by other compounds MX2 of transition metals M and chalcogens X = O, S, Se and Te. Also certain dipnictides with X standing for P, As and Sb etc. are known to adopt the pyrite structure.[13]

In the first bonding sphere, the Fe atoms are surrounded by six S nearest neighbours, in a distorted octahedral arrangement. The material is a diamagnetic semiconductor and the Fe ions should be considered to be in a low spin divalent state (as shown by Mössbauer spectroscopy as well as XPS), rather than a tetravalent state as the stoichiometry would suggest.

The positions of X ions in the pyrite structure may be derived from the fluorite structure, starting from a hypothetical Fe2+(S)2 structure. Whereas F ions in CaF2 occupy the centre positions of the eight subcubes of the cubic unit cell (¼ ¼ ¼) etc., the S ions in FeS2 are shifted from these high symmetry positions along <111> axes to reside on (uuu) and symmetry-equivalent positions. Here, the parameter u should be regarded as a free atomic parameter that takes different values in different pyrite-structure compounds (iron pyrite FeS2: u(S) = 0.385 [14]). The shift from fluorite u = 0.25 to pyrite u = 0.385 is rather large and creates a S-S distance that is clearly a binding one. This is not surprising as in contrast to F an ion S is not a closed shell species. It is isoelectronic with a chlorine atom, also undergoing pairing to form Cl2 molecules. Both low spin Fe2+ and the disulfide S22− moeties are closed shell entities, explaining the diamagnetic and semiconducting properties.

The S atoms have bonds with three Fe and one other S atom. The site symmetry at Fe and S positions is accounted for by point symmetry groups C3i and C3, respectively. The missing center of inversion at S lattice sites has important consequences for the crystallographic and physical properties of iron pyrite. These consequences derive from the crystal electric field active at the sulfur lattice site, which causes a polarisation of S ions in the pyrite lattice.[15] The polarisation can be calculated on the basis of higher-order Madelung constants and has to be included in the calculation of the lattice energy by using a generalised Born–Haber cycle. This reflects the fact that the covalent bond in the sulfur pair is inadequately accounted for by a strictly ionic treatment.

Arsenopyrite has a related structure with heteroatomic As-S pairs rather than homoatomic ones. Marcasite also possesses homoatomic anion pairs, but the arrangement of the metal and diatomic anions is different from that of pyrite. Despite its name a chalcopyrite does not contain dianion pairs, but single S2− sulfide anions.

Crystal habit Edit

File:Pyrite elbe.jpg

Pyrite usually forms cuboid crystals, sometimes forming in close association to form raspberry-like framboids. However, under certain circumstances, it can form anastamozing filaments or T-shaped crystals.[16] Pyrite can also form dodecahedral crystals and this suggests an explanation for the artificial geometrical models found in Europe as early as the 5th century BC.[17]

VarietiesEdit

Cattierite (Template:CobaltS2) and vaesite (NiS2) are similar in their structure and belong also to the pyrite group.

Bravoite is a nickel-cobalt bearing variety of pyrite, with > 50% substitution of Ni2+ for Fe2+ within pyrite. Bravoite is not a formally recognised mineral, and is named after Peruvian scientist Jose J. Bravo (1874–1928).[18]

Distinguishing similar mineralsEdit

It is distinguishable from native gold by its hardness, brittleness and crystal form. Natural gold tends to be anhedral (irregularly shaped), whereas pyrite comes as either cubes or multifaceted crystals. Chalcopyrite is brighter yellow with a greenish hue when wet and is softer (3.5–4 on Mohs' scale).[19] Arsenopyrite is silver white and does not become more yellow when wet.

HazardsEdit

File:GoldinPyriteDrainage acide.JPG

Iron pyrite is unstable in the natural environment: in nature it is always being created or being destroyed. Iron pyrite exposed to air and water decomposes into iron oxides and sulfate. This process is hastened by the action of Acidithiobacillus bacteria which oxidize the pyrite to produce ferrous iron and sulfate. These reactions occur more rapidly when the pyrite is in fine crystals and dust, which is the form it takes in most mining operations.

Acid drainageEdit

Sulfate released from decomposing pyrite combines with water, producing sulfuric acid, leading to acid rock drainage and potentially acid rain.

Dust explosionsEdit

Pyrite oxidation is sufficiently exothermic that underground coal mines in high-sulfur coal seams have occasionally had serious problems with spontaneous combustion in the mined-out areas of the mine. The solution is to hermetically seal the mined-out areas to exclude oxygen.[20]

In modern coal mines, limestone dust is sprayed onto the exposed coal surfaces to reduce the hazard of dust explosions. This has the secondary benefit of neutralizing the acid released by pyrite oxidation and therefore slowing the oxidation cycle described above, thus reducing the likelihood of spontaneous combustion. In the long term, however, oxidation continues, and the hydrated sulfates formed may exert crystallization pressure that can expand cracks in the rock and lead eventually to roof fall.[21]

Weakened building materialsEdit

Building stone containing pyrite tends to stain brown as the pyrite oxidizes. This problem appears to be significantly worse if any marcasite is present.[22] The presence of pyrite in the aggregate used to make concrete can lead to severe deterioration as the pyrite oxidizes.[23] In early 2009, problems with Chinese drywall imported into the United States after Hurricane Katrina were attributed to oxidation of pyrite.[24] In the United States, in Canada,[25] and more recently in Ireland,[26][27] where it was used as underfloor infill, pyrite contamination has caused major structural damage. Modern tests for aggregate materials[28] certify such materials as free of pyrite.

Pyritised fossilsEdit

File:Bullypyrite.jpg

Pyrite and marcasite commonly occur as replacement pseudomorphs after fossils in black shale and other sedimentary rocks formed under reducing environmental conditions.

File:Pyrite - disc.jpg

However, pyrite dollars or pyrite suns which have an appearance similar to sand dollars are pseudofossils and lack the pentagonal symmetry of the animal.

ReferencesEdit

  1. Script error
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  3. Energizer Corporation, Lithium Iron Disulfide
  4. Script error
  5. The Principles Underlying Radio Communication, Radio Pamphlet No. 40, U.S. Army Signal Corps, Dec. 10 (1918) section 179, pp. 302–305.
  6. Thomas H. Lee, The Design of Radio Frequency Integrated Circuits, 2nd Ed., Cambridge University Press (2004) pp. 4–6.
  7. Script error
  8. Cheaper materials could be key to low-cost solar cells by Robert Sanders, 17 February 2009
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  10. Vaughan, D. J.; Craig, J. R. "Mineral Chemistry of Metal Sulfides" Cambridge University Press, Cambridge (1978) ISBN 0-521-21489-0
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  17. Dana J. et al.,(1944), System of mineralogy, New York, p 282
  18. Mindat – bravoite. Mindat.org (2011-05-18). Retrieved on 2011-05-25.
  19. Pyrite on. Minerals.net (2011-02-23). Retrieved on 2011-05-25.
  20. Andrew Roy, Coal Mining in Iowa, Coal Trade Journal, quoted in History of Lucas County Iowa, State Historical Company, Des Moines (1881) pp. 613–615.
  21. Script error
  22. Oliver Bowles, The Structural and Ornamental Stones of Minnesota, Bulletin 663, United States Geological Survey, Washington (1918) p. 25.
  23. Script error
  24. William Angelo, A Material Odor Mystery Over Foul-Smelling Drywall, from the web site of Engineering News Record Construction, dated 1/28/2009.
  25. "PYRITE and Your House, What Home-Owners Should Know" – ISBN 2-922677-01-X - Legal deposit – National Library of Canada, May 2000
  26. The Irish Times – Saturday, June 11, 2011 – Homeowners in protest over pyrite damage to houses (Subscription required)
  27. Irish Independent — 22 February 2010 (Michael Brennan) Devastating 'pyrite epidemic' hits 20,000 newly built houses
  28. I.S. EN 13242:2002 Aggregates for unbound and hydraulically bound materials for use in civil engineering work and road construction

Further readingEdit

  • American Geological Institute, 2003, Dictionary of Mining, Mineral, and Related Terms, 2nd ed., Springer, New York, ISBN 978-3-540-01271-9
  • David Rickard, Pyrite: A Natural History of Fool's Gold, Oxford, New York, 2015, ISBN 978-0-19-020367-2

External linksEdit

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