Nickel sulfide

Nickel sulfide
Names

IUPAC name Nickel(II) sulfide
Other names nickel sulfide, nickel monosulfide, nickelous sulfide
Identifiers
CAS Number	11113-75-0^Y
3D model (JSmol)	Interactive image Interactive image
ChemSpider	26134
ECHA InfoCard	100.037.113
EC Number	234-349-7
PubChem CID	28094
RTECS number	QR9705000
UNII	I6929D52YQ^Y
CompTox Dashboard (EPA)	DTXSID5036921
SMILES [Ni]=S [Ni+2].[S-2]
Properties
Chemical formula	NiS
Molar mass	90.7584 g mol⁻¹
Appearance	black 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)
Solubility in water	insoluble
Solubility	degraded by nitric acid
Magnetic susceptibility (χ)	+190.0·10⁻⁶ cm³/mol
Structure
Crystal structure	hexagonal
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	may cause cancer by inhalation
GHS labelling:
Pictograms
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Y verify (what is ^YN ?) Infobox references

Chemical compound

Nickel sulfide is any inorganic compound with the formula NiS_x. 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.

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
Nickel	Sulfur

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]

In glass manufacturing

Float glass contains a small amount of nickel sulfide, formed from the sulfur in the fining agent Na
₂SO
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]

References

^ ^a ^b Kerfoot, Derek G. E. (2005). "Nickel". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_157. ISBN 978-3527306732.
^ Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
^ 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.
^ "NiS and Spontaneous Breakage". Glass on Web. Nov 2012. Archived from the original on 2013-06-12.
^ 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.
^ O.Glemser "Nickel Sulfide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 2. p. 1551.
^ 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
^ Gamsjager H. C., Bugajski J., Gajda T., Lemire R. J., Preis W. (2005) Chemical Thermodynamics of Nickel, Amsterdam, Elsevier B.V.
^ ^a ^b 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.
^ Barry, John (12 January 2006). "The Achille Heel of a Wonderful Material: Toughened Glass". Glass on Web. Retrieved 16 August 2019.