nickel sulfide
{{redirect|NiS2|the European regulation|Cyber-security regulation#NIS 2 Directive}}
{{Chembox
| Name =
| ImageFile = Nickel-sulfide-xtal-unit-cell-3D-bs-17.png
| verifiedrevid = 477162765
| IUPACName = Nickel(II) sulfide
| OtherNames = nickel sulfide, nickel monosulfide, nickelous sulfide
| Section2 = {{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 11113-75-0
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = I6929D52YQ
| ChemSpiderID = 26134
| EINECS = 234-349-7
| PubChem = 28094
| RTECS = QR9705000
| SMILES = [Ni]=S
| SMILES1 = [Ni+2].[S-2]
}}
| Section3 = {{Chembox Properties
| Formula = {{Chem|NiS}}
| MolarMass = 90.7584 g mol−1
| Appearance = black solid
| Odor = Odorless
| Density = 5.87 g/cm3
| MeltingPtC = 797
| BoilingPtC = 1388
| Solubility = insoluble
| SolubleOther = degraded by nitric acid
| VaporPressure =
| pKa =
| MagSus = +190.0·10−6 cm3/mol
}}
| Section4 = {{Chembox Structure
| CrystalStruct = hexagonal
}}
| Section7 = {{Chembox Hazards
| GHSPictograms = {{GHS exclamation mark}}
| MainHazards = may cause cancer by inhalation
}}
}}
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), polydymite (Ni3S4), and vaesite (NiS2).{{Ullmann|author=Kerfoot, Derek G. E. |title=Nickel|doi=10.1002/14356007.a17_157|year=2005}} Some nickel sulfides are used commercially as catalysts.
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.Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. {{ISBN|0-19-855370-6}}.
| class="wikitable" style="text-align:center;"
|+Coordination environments in nickel sulfide |
| Nickel
! Sulfur |
|---|
| 150px
| 150px |
| octahedral |
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 {{convert|379|C|F}}, and converts into the β-phase at lower temperatures. That phase transition causes an increase in volume by 2–4%.{{cite journal | doi = 10.1016/S0025-5408(98)00121-4 | title = Raman spectra of nickel(II) sulfide | year = 1998 | last1 = Bishop | first1 = D.W. | last2 = Thomas | first2 = P.S. | last3 = Ray | first3 = A.S. | journal = Materials Research Bulletin | volume = 33 | issue = 9 | pages = 1303}}{{cite web | title = NiS and Spontaneous Breakage | url = http://www.glassonweb.com/articles/article/96/ | publisher = Glass on Web | date = Nov 2012 | url-status = dead | archive-url = https://web.archive.org/web/20130612022942/http://www.glassonweb.com/articles/article/96 | archive-date = 2013-06-12 }}{{cite journal |last1=Bonati |first1=Antonio |last2=Pisano |first2=Gabriele |last3=Royer Carfagni |first3=Gianni |title=A statistical model for the failure of glass plates due to nickel sulfide inclusions |journal=Journal of the American Ceramic Society |date=12 October 2018 |volume=102 |issue=5 |pages=2506–2521 |doi=10.1111/jace.16106 |s2cid=140055629 }}
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:O.Glemser "Nickel Sulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 2. p. 1551.
: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.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}}
The most commonly practiced reaction of nickel sulfides involves conversion to nickel oxides. This conversion involves heating the sulfide ores in air:
:{{Chem2|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.Gamsjager H. C., Bugajski J., Gajda T., Lemire R. J., Preis W. (2005) Chemical Thermodynamics of Nickel, Amsterdam, Elsevier B.V.
File:Millerite-Chalcopyrite-Calcite-284770.jpg 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).
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=In glass manufacturing=
Float glass contains a small amount of nickel sulfide, formed from the sulfur in the fining agent {{chem|Na|2|S|O|4}} and the nickel contained in metallic alloy contaminants.{{cite journal |last1=Karlsson |first1=Stefan |title=Spontaneous fracture in thermally strengthened glass – A review & outlook |journal=Ceramics – Silikaty |date=30 April 2017 |pages=188–201 |doi=10.13168/cs.2017.0016 |url=https://www.researchgate.net/publication/316596288 |access-date=16 August 2019|doi-access=free }}
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.{{cite web |last1=Barry |first1=John |title=The Achille Heel of a Wonderful Material: Toughened Glass |url=https://www.glassonweb.com/article/achille-heel-wonderful-material-toughened-glass |website=Glass on Web |access-date=16 August 2019 |date=12 January 2006}} That spontaneous fracture occurs years or decades after glass manufacturing.
References
{{Reflist|colwidth=30em}}
{{Nickel compounds}}
{{Sulfides}}