Nickel sulfide

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Nickel sulfide
Nickel-sulfide-xtal-unit-cell-3D-bs-17.png
Names
IUPAC name
Nickel(II) sulfide
Other names
nickel sulfide, nickel monosulfide, nickelous sulfide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.037.113 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-349-7
PubChem CID
RTECS number
  • QR9705000
UNII
  • [Ni]=S
  • [Ni+2].[S-2]
Properties
NiS
Molar mass 90.7584 g mol−1
Appearanceblack solid
Odor Odorless
Density 5.87 g/cm3
Melting point 797 °C (1,467 °F; 1,070 K)
Boiling point 1,388 °C (2,530 °F; 1,661 K)
insoluble
Solubility degraded by nitric acid
+190.0·10−6 cm3/mol
Structure
hexagonal
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
may cause cancer by inhalation
GHS labelling:
GHS-pictogram-exclam.svg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Nickel sulfide is any inorganic compound with the formula NixSy. These compounds range in color from bronze (Ni3S2) to black (NiS2). The nickel sulfide with simplest stoichiometry is NiS, also known as the mineral millerite. From the economic perspective, Ni9S8, the mineral pentlandite, is the chief source of mined nickel. Other minerals include heazlewoodite (Ni3S2) and polydymite (Ni3S4), and the mineral Vaesite (NiS2). [1] Some nickel sulfides are used commercially as catalysts.

Contents

Structure

Like many related materials, nickel sulfide adopts the nickel arsenide motif. In this structure, nickel is octahedral and the sulfide centers are in trigonal prismatic sites. [2]

Coordination environments in nickel sulfide
NickelSulfur
Nickel-sulfide-xtal-Ni-coordination-3D-bs-17.png Nickel-sulfide-xtal-S-coordination-3D-bs-17.png
octahedral trigonal prismatic

NiS has two polymorphs. The α-phase has a hexagonal unit cell, while the β-phase has a rhombohedral cell. The α-phase is stable at temperatures above 379 °C (714 °F), and converts into the β-phase at lower temperatures. That phase transition causes an increase in volume by 2–4%. [3] [4] [5]

Synthesis and reactions

The precipitation of solid black nickel sulfide is a mainstay of traditional qualitative inorganic analysis schemes, which begins with the separation of metals on the basis of the solubility of their sulfides. Such reactions are written: [6]

Ni2+ + H2S → NiS + 2 H+

Many other more controlled methods have been developed, including solid state metathesis reactions (from NiCl2 and Na2S) and high temperature reactions of the elements. [7]

The most commonly practiced reaction of nickel sulfides involves conversion to nickel oxides. This conversion involves heating the sulfide ores in air: [1]

NiS + 1.5 O2 → NiO + SO2

Occurrence

Natural

The mineral millerite is also a nickel sulfide with the molecular formula NiS, although its structure differs from synthetic stoichiometric NiS due to the conditions under which it forms. It occurs naturally in low temperature hydrothermal systems, in cavities of carbonate rocks, and as a byproduct of other nickel minerals. [8]

Millerite crystals Millerite-Chalcopyrite-Calcite-284770.jpg
Millerite crystals

In nature, nickel sulfides commonly occur as solid solutions with iron sulfides in minerals such as pentlandite and pyrrhotite. These minerals have the formula Fe9-xNixS8 and Fe7-xNixS6, respectively. In some cases they are high in nickel (larger values of x).

In glass manufacturing

Float glass contains a small amount of nickel sulfide, formed from the sulfur in the fining agent Na
2
SO
4
and the nickel contained in metallic alloy contaminants. [9]

Nickel sulfide inclusions are a problem for tempered glass applications. After the tempering process, nickel sulfide inclusions are in the metastable alpha phase. The inclusions eventually convert to the beta phase (stable at low temperature), increasing in volume and causing cracks in the glass. In the middle of tempered glass, the material is under tension, which causes the cracks to propagate and leads to spontaneous glass fracture. [10] That spontaneous fracture occurs years or decades after glass manufacturing. [9]

Related Research Articles

<span class="mw-page-title-main">Pentlandite</span> Iron–nickel sulfide

Pentlandite is an iron–nickel sulfide with the chemical formula (Fe,Ni)9S8. Pentlandite has a narrow variation range in nickel to iron ratios (Ni:Fe), but it is usually described as 1:1. In some cases, this ratio is skewed by the presence of pyrrhotite inclusions. It also contains minor cobalt, usually at low levels as a fraction of weight.

Sulfide (also sulphide in British English ) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH) are the conjugate acids of sulfide.

<span class="mw-page-title-main">Molybdenum disulfide</span> Chemical compound

Molybdenum disulfide is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is MoS
2
.

<span class="mw-page-title-main">Silver sulfide</span> Chemical compound

Silver sulfide is an inorganic compound with the formula Ag
2
S
. A dense black solid, it is the only sulfide of silver. It is useful as a photosensitizer in photography. It constitutes the tarnish that forms over time on silverware and other silver objects. Silver sulfide is insoluble in most solvents, but is degraded by strong acids. Silver sulfide is a network solid made up of silver and sulfur where the bonds have low ionic character.

<span class="mw-page-title-main">Nickeline</span> Nickel arsenide mineral

Nickeline or niccolite is a mineral consisting primarily of nickel arsenide (NiAs). The naturally-occurring mineral contains roughly 43.9% nickel and 56.1% arsenic by mass, but composition of the mineral may vary slightly.

<span class="mw-page-title-main">Pyrrhotite</span> Magnetic iron sulfide mineral

Pyrrhotite is an iron sulfide mineral with the formula Fe(1-x)S. 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 is weakly magnetic. The magnetism decreases as the iron content increases, and troilite is non-magnetic. Pyrrhotite is generally tabular and brassy/bronze in color with a metallic luster. The mineral occurs with mafic igneous rocks like norites, and may form from pyrite during metamorphic processes. Pyrrhotite is associated and mined with other sulfide minerals like pentlandite, pyrite, chalcopyrite, and magnetite, and has been found globally.

<span class="mw-page-title-main">Polysulfide</span> Molecules derived from sulfur chains

Polysulfides are a class of chemical compounds derived from anionic chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. The inorganic polysulfides have the general formula S2−
n
. These anions are the conjugate bases of polysulfanes H2Sn. Organic polysulfides generally have the formulae R1SnR2, where R is an alkyl or aryl group.

<span class="mw-page-title-main">Sulfide mineral</span> Class of minerals containing sulfide or disulfide as the major anion

The sulfide minerals are a class of minerals containing sulfide (S2−) or disulfide as the major anion. Some sulfide minerals are economically important as metal ores. The sulfide class also includes the selenides, the tellurides, the arsenides, the antimonides, the bismuthinides, the sulfarsenides and the sulfosalts. Sulfide minerals are inorganic compounds.

<span class="mw-page-title-main">Chalcogenide</span>

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

<span class="mw-page-title-main">Copper monosulfide</span> Chemical compound

Copper monosulfide is a chemical compound of copper and sulfur. It was initially thought to occur in nature as the dark indigo blue mineral covellite. However, it was later shown to be rather a cuprous compound, formula Cu+3S(S2). CuS is a moderate conductor of electricity. A black colloidal precipitate of CuS is formed when hydrogen sulfide, H2S, is bubbled through solutions of Cu(II) salts. It is one of a number of binary compounds of copper and sulfur (see copper sulfide for an overview of this subject), and has attracted interest because of its potential uses in catalysis and photovoltaics.

<span class="mw-page-title-main">Siegenite</span>

Siegenite (also called grimmite, or nickel cobalt sulfide) is a ternary transition metal dichalcogenide compound with the chemical formula (Ni,Co)3S4. It has been actively studied as a promising material system for electrodes in electrochemical energy applications due to its better conductivity, greater mechanical and thermal stability, and higher performance compared to metal oxides currently in use. Potential applications of this material system include supercapacitors, batteries, electrocatalysis, dye-sensitized solar cells, photocatalysis, glucose sensors, and microwave absorption.

<span class="mw-page-title-main">Tin(IV) sulfide</span> Chemical compound

Tin(IV) sulfide is a compound with the formula Sn S
2
. The compound crystallizes in the cadmium iodide motif, with the Sn(IV) situated in "octahedral holes' defined by six sulfide centers. It occurs naturally as the rare mineral berndtite. It is useful as semiconductor material with band gap 2.2 eV.

<span class="mw-page-title-main">Gaspéite</span> Nickel carbonate mineral

Gaspéite, a very rare nickel carbonate mineral, with the formula (Ni,Fe,Mg)CO3, is named for the place it was first described, in the Gaspé Peninsula, Québec, Canada.

A nickel sulfide inclusion,, occurs during the process of manufacturing float glass.

<span class="mw-page-title-main">Mackinawite</span> Iron nickel sulfide mineral

Mackinawite is an iron nickel sulfide mineral with the chemical formula (Fe,Ni)
1+x
S
. The mineral crystallizes in the tetragonal crystal system and has been described as a distorted, close packed, cubic array of S atoms with some of the gaps filled with Fe. Mackinawite occurs as opaque bronze to grey-white tabular crystals and anhedral masses. It has a Mohs hardness of 2.5 and a specific gravity of 4.17. It was first described in 1962 for an occurrence in the Mackinaw mine, Snohomish County, Washington for which it was named.

<span class="mw-page-title-main">Cobalt sulfide</span> Chemical compound

Cobalt sulfide is the name for chemical compounds with a formula CoxSy. Well-characterized species include minerals with the formulas CoS, CoS2, Co3S4, and Co9S8. In general, the sulfides of cobalt are black, semiconducting, insoluble in water, and nonstoichiometric.

<span class="mw-page-title-main">Nickel selenide</span> Chemical compound

Nickel selenide is the inorganic compound with the formula NiSe. As for many metal chalcogenides, the phase diagram for nickel(II) selenide is complicated. Two other selenides of nickel are known, NiSe2 with a pyrite structure, and Ni2Se3. Additionally, NiSe is usually nonstoichiometric and is often described with the formula Ni1−xSe, with 0 < x < 0.15. This material is a semi-conducting solid, and can be obtained as in the form of a black fine powder, or silver if obtained in the form of larger crystals. Nickel(II) selenide is insoluble in all solvents, but can be degraded by strongly oxidizing acids.

<span class="mw-page-title-main">Millerite</span> Nickel sulfide mineral

Millerite or nickel blende is a nickel sulfide mineral, NiS. 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 lack of association with pyrite or pyrrhotite.

<span class="mw-page-title-main">Gallium(III) sulfide</span> Chemical compound

Gallium(III) sulfide, Ga2S3, is a compound of sulfur and gallium, that is a semiconductor that has applications in electronics and photonics.

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

References

  1. 1 2 Kerfoot, Derek G. E. (2005). "Nickel". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_157. ISBN   978-3527306732.
  2. Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN   0-19-855370-6.
  3. Bishop, D.W.; Thomas, P.S.; Ray, A.S. (1998). "Raman spectra of nickel(II) sulfide". Materials Research Bulletin. 33 (9): 1303. doi:10.1016/S0025-5408(98)00121-4.
  4. "NiS and Spontaneous Breakage". Glass on Web. Nov 2012. Archived from the original on 2013-06-12.
  5. Bonati, Antonio; Pisano, Gabriele; Royer Carfagni, Gianni (12 October 2018). "A statistical model for the failure of glass plates due to nickel sulfide inclusions". Journal of the American Ceramic Society. 102 (5): 2506–2521. doi:10.1111/jace.16106. S2CID   140055629.
  6. O.Glemser "Nickel Sulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 2. p. 1551.
  7. leading reference can be found in: Shabnam Virji, Richard B. Kaner, Bruce H. Weiller "Direct Electrical Measurement of the Conversion of Metal Acetates to Metal Sulfides by Hydrogen Sulfide" Inorg. Chem., 2006, 45 (26), pp 10467–10471. doi : 10.1021/ic0607585
  8. Gamsjager H. C., Bugajski J., Gajda T., Lemire R. J., Preis W. (2005) Chemical Thermodynamics of Nickel, Amsterdam, Elsevier B.V.
  9. 1 2 Karlsson, Stefan (30 April 2017). "Spontaneous fracture in thermally strengthened glass – A review & outlook". Ceramics – Silikaty: 188–201. doi: 10.13168/cs.2017.0016 . Retrieved 16 August 2019.
  10. Barry, John (12 January 2006). "The Achille Heel of a Wonderful Material: Toughened Glass". Glass on Web. Retrieved 16 August 2019.