Pyrite

The mineral pyrite, or iron pyrite, also known as fool's gold, is an iron sulfide with the chemical formula FeS₂. Pyrite is the most abundant sulfide mineral.
File:2780M-pyrite1.jpg|thumb|Pyrite cubic crystals on marl from Navajún, La Rioja, Spain
Pyrite'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.
The name pyrite is derived from the Greek πυρίτης λίθος, 'stone or mineral which strikes fire', in turn from πῦρ, 'fire'. 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 is now called pyrite.
By Georgius Agricola's time,, the term had become a generic term for all of the sulfide minerals.
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, but has also been identified in the sclerites of scaly-foot gastropods. Despite being nicknamed "fool's gold", pyrite is sometimes found in association with small quantities of gold. A substantial proportion of the gold is "invisible gold" incorporated into the pyrite. It has been suggested that the presence of both gold and arsenic is a case of coupled substitution but as of 1997 the chemical state of the gold remained controversial.

Uses

Pyrite gained a brief popularity in the 16th and 17th centuries as a source of ignition in early firearms, most notably the wheellock, where a sample of pyrite was placed against a circular file to strike the sparks needed to fire the gun.
The Kaurna people of South Australia use pyrite with flintstone and a form of tinder made of stringybark as a traditional method of starting fires.
Pyrite has been used since classical times to manufacture copperas. Iron pyrite was heaped up and allowed to weather. The acidic runoff from the heap was then boiled with iron to produce iron sulfate. In the 15th century, new methods of 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.
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 and elemental sulfur starts at ; at around, p_S₂ is about.
A newer commercial use for pyrite is as the cathode material in Energizer brand non-rechargeable lithium metal batteries.
Pyrite is a semiconductor material with a band gap of 0.95 eV. Pure pyrite is naturally n-type, in both crystal and thin-film forms, potentially due to sulfur vacancies in the pyrite crystal structure acting as n-dopants.
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.
Pyrite has been proposed as an abundant, non-toxic, inexpensive material in low-cost photovoltaic solar panels. Synthetic iron sulfide was used with copper sulfide to create the photovoltaic material. More recent efforts are working toward thin-film solar cells made entirely of pyrite.
Pyrite is used to make marcasite jewelry. Marcasite jewelry, using small faceted pieces of pyrite, often set in silver, has been made since ancient times and was popular in the Victorian era. 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. The specimens of pyrite, when it appears as good quality crystals, are used in decoration. They are also very popular in mineral collecting. Among the sites that provide the best specimens are Soria and La Rioja provinces.
In value terms, China constitutes the largest market for imported unroasted iron pyrites worldwide, making up 65% of global imports. China is also the fastest growing in terms of the unroasted iron pyrites imports, with a CAGR of +27.8% from 2007 to 2016.

Research

In July 2020 scientists reported that they have observed a voltage-induced transformation of normally diamagnetic pyrite into a ferromagnetic material, which may lead to applications in devices such as solar cells or magnetic data storage.
Researchers at Trinity College Dublin, Ireland have demonstrated that FeS₂ can be exfoliated into few-layers just like other two-dimensional layered materials such as graphene by a simple liquid-phase exfoliation route. This is the first study to demonstrate the production of non-layered 2D-platelets from 3D bulk FeS₂. Furthermore, they have used these 2D-platelets with 20% single walled carbon-nanotube as an anode material in lithium-ion batteries, reaching a capacity of 1000 mAh/g close to the theoretical capacity of FeS₂.
In 2021, a natural pyrite stone has been crushed and pre-treated followed by liquid-phase exfoliation into two-dimensional nanosheets, which has shown capacities of 1200 mAh/g as an anode in lithium-ion batteries.

Formal oxidation states for pyrite, marcasite, molybdenite and arsenopyrite

From the perspective of classical inorganic chemistry, which assigns formal oxidation states to each atom, pyrite and marcasite are probably best described as Fe²⁺²⁻. 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, MoS₂, features isolated sulfide S²⁻ centers and the oxidation state of molybdenum is Mo⁴⁺. The mineral arsenopyrite has the formula FeAsS. Whereas pyrite has ²⁻ units, arsenopyrite has ³⁻ units, formally derived from deprotonation of arsenothiol. Analysis of classical oxidation states would recommend the description of arsenopyrite as Fe³⁺³⁻.

Crystallography

Iron-pyrite FeS₂ represents the prototype compound of the crystallographic pyrite structure. The structure is cubic and was among the first crystal structures solved by X-ray diffraction. It belongs to the crystallographic space group Pa and is denoted by the Strukturbericht notation C2. Under thermodynamic standard conditions the lattice constant of stoichiometric iron pyrite FeS₂ amounts to. The unit cell is composed of a Fe face-centered cubic sublattice into which the ions are embedded. The pyrite structure is also seen in other MX₂ compounds of transition metals M and chalcogens X = O, S, Se and Te. Certain dipnictides with X standing for P, As and Sb etc. are also known to adopt the pyrite structure.
The Fe atoms are bonded to six S atoms, giving a distorted octahedron. The material is a semiconductor. The Fe ions are usually considered to be low spin divalent state. The material as a whole behaves as a Van Vleck paramagnet, despite its low-spin divalency.
The sulfur centers occur in pairs, described as. Reduction of pyrite with potassium gives potassium dithioferrate, KFeS₂. This material features ferric ions and isolated sulfide centers.
The S atoms are tetrahedral, being bonded to three Fe centers and one other S atom. The site symmetry at Fe and S positions is accounted for by point symmetry groups C_3i 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 polarization of S ions in the pyrite lattice. 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 S-S pairs. Marcasite also possesses homoatomic anion pairs, but the arrangement of the metal and diatomic anions differs from that of pyrite. Despite its name, chalcopyrite does not contain dianion pairs, but single S²⁻ sulfide anions.

Crystal habit

Pyrite usually forms cuboid crystals, sometimes forming in close association to form raspberry-shaped masses called framboids. However, under certain circumstances, it can form anastomosing filaments or T-shaped crystals. Pyrite can also form shapes almost the same as a regular dodecahedron, known as pyritohedra, and this suggests an explanation for the artificial geometrical models found in Europe as early as the 5th century BC.

Varieties

, vaesite and hauerite, as well as sperrylite are similar in their structure and belong also to the pyrite group.
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 the Peruvian scientist Jose J. Bravo.