Nickel(II) oxide: Difference between revisions

{{Short description|Chemical compound}}

| verifiedrevid = 442344985

| ImageName = Nickel(II) oxide

| ImageName2 = Nickel(II) oxide

| OtherNames = Nickel monoxide <br> Oxonickel

|Section1={{Chembox Identifiers

| CASNo = 1313-99-1

| CASNo_Ref = {{cascite|correct|CAS}}

| ChemSpiderID = 156595

| EINECS = 215-215-7

| PubChem = 14805

| RTECS = QR8400000

| UNNumber = 3288 3077

| UNII_Ref = {{fdacite|correct|FDA}}

| UNII = C3574QBZ3Y

| StdInChI = 1S/Ni.O/q+2;-2

| StdInChIKey = KVAWBJDCAFOHRG-UHFFFAOYSA-N

| SMILES = [O-2].[Ni+2]

|Section2={{Chembox Properties

| Formula = NiO

| MolarMass = 74.6928 g/mol

| Appearance = green crystalline solid

| Density = 6.67 g/cm³

| Solubility = negligible

| SolubleOther = dissolves in [[potassium cyanide|KCN]]

| MeltingPtC = 1955

| BoilingPt =

| RefractIndex = 2.1818

| MagSus = +660.0·10⁻⁶ cm³/mol }}

|Section3={{Chembox Structure

| Coordination =

| CrystalStruct =

| Dipole =

|Section4={{Chembox Thermochemistry

| DeltaHf = -240.0 kJ/mol}}

|Section7={{Chembox Hazards

| ExternalSDS = [http://hazard.com/msds/mf/baker/baker/files/n3060.htm JT Baker]

| GHS_ref=<ref>{{cite web |title=Nickel oxide |url=https://pubchem.ncbi.nlm.nih.gov/compound/14805#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en}}</ref>

| GHSPictograms = {{GHS07}}{{GHS08}}{{GHS09}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|317|350|372|413}}

| PPhrases = {{P-phrases|201|202|260|261|264|270|272|273|280|281|285|302+352|304+341|308+313|314|321|333+313|342+311|363|391|405|501}}

| NFPA_ref = <ref>{{cite web|url=https://www.nwmissouri.edu/naturalsciences/sds/n/Nickel%20II%20oxide.pdf |title=Safety Data Sheet |website=[[Northwest Missouri State University]]}}</ref>

| NFPA-H = 2

| NFPA-R = 0

| NFPA-F = 0

| NFPA-S =

| FlashPt = Non-flammable

| LD50 =

| LDLo = 5000 mg/kg (rat, oral)<ref>{{IDLH|7440020|Nickel metal and other compounds (as Ni)}}</ref>

|Section8={{Chembox Related

| OtherAnions = [[Nickel(II) sulfide]]<br/>[[Nickel(II) selenide]]<br />[[Nickel(II) telluride]]

| OtherCations = [[Palladium(II) oxide]]

| OtherCompounds =

'''Nickel(II) oxide''' is the [[chemical compound]] with the formula {{chem|Ni|O}}. It is the principal oxide of [[nickel]].<ref name="Greenwood">{{Greenwood&Earnshaw1st|pages=1336–37}}</ref> It is classified as a basic metal oxide. Several million kilograms are produced annually of varying quality, mainly as an intermediate in the production of nickel alloys.<ref name=Ullmann>{{Ullmann|doi=10.1002/14356007.a17_157|isbn=3527306730|title=Nickel|year=2000|last1=Kerfoot|first1=Derek G. E.}}</ref> The mineralogical form of {{chem|Ni|O}}, [[bunsenite]], is very rare. Other [[nickel(III) oxide]]s have been claimed, for example: {{chem|Ni|2|O|3}} and {{chem|Ni|O|2}}, but remain unproven.<ref name="Greenwood"/>

{{chem|Ni|O}} can be prepared by multiple methods. Upon heating above 400&nbsp;°C, nickel powder reacts with oxygen to give {{chem|Ni|O}}. In some commercial processes, green nickel oxide is made by heating a mixture of nickel powder and water at 1000&nbsp;°C; the rate for this reaction can be increased by the addition of {{chem|Ni|O}}.<ref name=Prad>"Handbook of Inorganic Chemicals", Pradniak, Pradyot; McGraw-Hill Publications,2002</ref> The simplest and most successful method of preparation is through pyrolysis of nickel(II) compounds such as the hydroxide, [[nickel nitrate|nitrate]], and [[nickel carbonate|carbonate]], which yield a light green powder.<ref name="Greenwood" /> Synthesis from the elements by heating the metal in oxygen can yield grey to black powders which indicates [[non-stoichiometric compound|nonstoichiometry]].<ref name="Greenwood" />

{{chem|Ni|O}} adopts the {{chem|Na|Cl}} structure, with [[octahedral]] Ni²⁺ and O^2&minus; sites. The conceptually simple structure is commonly known as the rock salt structure. Like many other binary metal oxides, {{chem|Ni|O}} is often non-stoichiometric, meaning that the Ni:O ratio deviates from 1:1. In nickel oxide, this non-stoichiometry is accompanied by a color change, with the stoichiometrically correct NiO being green and the non-stoichiometric {{chem|Ni|O}} being black.

{{chem|Ni|O}} has a variety of specialized applications and generally, applications distinguish between "chemical grade", which is relatively pure material for specialty applications, and "metallurgical grade", which is mainly used for the production of alloys. It is used in the ceramic industry to make frits, ferrites, and porcelain glazes. The sintered oxide is used to produce nickel steel alloys. [[Charles Édouard Guillaume]] won the 1920 [[Nobel Prize in Physics]] for his work on nickel steel alloys which he called [[invar]] and [[elinvar]].

{{chem|Ni|O}} is a commonly used hole transport material in thin film solar cells.<ref>{{cite journal |last1=Di Girolamo |first1=Diego |last2=Matteocci |first2=Fabio |last3=Kosasih |first3=Felix Utama |last4=Chistiakova |first4=Ganna |last5=Zuo |first5=Weiwei |last6=Divitini |first6=Giorgio |last7=Korte |first7=Lars |last8=Ducati |first8=Caterina |last9=Di Carlo |first9=Aldo |last10=Dini |first10=Danilo |last11=Abate |first11=Antonio |title=Stability and Dark Hysteresis Correlate in NiO‐Based Perovskite Solar Cells |journal=Advanced Energy Materials |date=August 2019 |volume=9 |issue=31 |pages=1901642 |doi=10.1002/aenm.201901642|s2cid=199076776 |url=http://www.helmholtz-berlin.de/pubbin/oai_publication?VT=1&ID=100950 }}</ref> It was also a component in the [[nickel-iron battery]], also known as the Edison Battery, and is a component in [[fuel cells]]. It is the precursor to many nickel salts, for use as [[specialty chemicals]] and catalysts. More recently, {{chem|Ni|O}} was used to make the NiCd rechargeable batteries found in many electronic devices until the development of the environmentally superior NiMH battery.<ref name=Prad/> {{chem|Ni|O}} an anodic [[electrochromism|electrochromic]] material, have been widely studied as counter electrodes with tungsten oxide, cathodic electrochromic material, in complementary [[electrochromic devices]].

About 4000 tons of chemical grade {{chem|Ni|O}} are produced annually.<ref name=Ullmann/> Black {{chem|Ni|O}} is the precursor to nickel salts, which arise by treatment with mineral acids. {{chem|Ni|O}} is a versatile hydrogenation catalyst.

Heating nickel oxide with either hydrogen, carbon, or carbon monoxide reduces it to metallic nickel. It combines with the oxides of sodium and potassium at high temperatures (>700&nbsp;°C) to form the corresponding [[nickelate]].<ref name=Prad/>

==Electronic structure==

NiO is useful for illustrating the failure of [[density functional theory]] (using functionals based on the [[local-density approximation]]) and [[Hartree–Fock theory]] to account for the [[strong correlation]]. The term strong correlation refers to behavior of electrons in solids that is not well described (often not even in a qualitatively correct manner) by simple one-electron theories such as the local-density approximation (LDA) or Hartree–Fock theory.<ref>{{Cite journal|last=Hüfner|first=S.|date=1994-04-01|title=Electronic structure of NiO and related 3d-transition-metal compounds|journal=Advances in Physics|volume=43|issue=2|pages=183–356|doi=10.1080/00018739400101495|issn=0001-8732|bibcode=1994AdPhy..43..183H}}</ref>{{citation needed|date=August 2019}} For instance, the seemingly simple material NiO has a partially filled 3d-band (the Ni atom has 8 of 10 possible 3d-electrons) and therefore would be expected to be a good conductor. However, strong Coulomb repulsion (a correlation effect) between d-electrons makes NiO instead a wide band gap [[Mott insulator]]. Thus, NiO has an electronic structure that is neither simply free-electron-like nor completely ionic, but a mixture of both.<ref>{{Cite journal|last1=Kuiper|first1=P.|last2=Kruizinga|first2=G.|last3=Ghijsen|first3=J.|last4=Sawatzky|first4=G. A.|last5=Verweij|first5=H.|date=1989|title=Character of Holes in Li_xNi_1−xO and Their Magnetic Behavior|journal=Physical Review Letters|volume=62|issue=2|pages=221–224|doi=10.1103/physrevlett.62.221|pmid=10039954|issn=0031-9007|bibcode=1989PhRvL..62..221K}}</ref><ref>{{Cite journal|last=Mott|first=N. F.|date=1949|title=The Basis of the Electron Theory of Metals, with Special Reference to the Transition Metals|journal=Proceedings of the Physical Society. Section A|language=en|volume=62|issue=7|pages=416–422|doi=10.1088/0370-1298/62/7/303|issn=0370-1298|bibcode=1949PPSA...62..416M}}</ref>

==Health risks==

The calculated half-life of dissolution of NiO in the blood is more than 90 days.<ref name=":0">English, J.C., Parker, R.D.R., Sharma, R.P. & Oberg, S.G. (1981). Toxicokinetics of nickel in rats after intratracheal administration of a soluble and insoluble form. Am Ind Hyg Assoc J. 42(7):486-492.</ref> NiO has a long retention half-time in the lungs; after administration to rodents, it persisted in the lungs for more than 3 months.<ref>Benson, J.M., Barr, E.B., Bechtold, W.E., Cheng, Y-S., Dunnick, J.K., Eastin, W.E., Hobbs, C.H., Kennedy, C.H. & Maples, K.R. (1994). The fate of inhaled nickel oxide and nickel subsurface in F344/N rats. Inhal Toxicol 6(2):167-183.</ref><ref name=":0" /> Nickel oxide is classified as a human carcinogen<ref name=":1">National Toxicology Program (NTP) (1996). Toxicology and Carcinogenesis Studies of Nickel Oxide (CAS No. 1313-99-1) in F344 Rats and B6C3F1 Mice (inhalation studies) US DHHS. ''NTP TR 451.'' NIH Publication No.96-3367.</ref><ref>Sunderman, F.W., Hopfer, S.M., Knight, J.A., Mccully, K.S., Cecutti, A.G., Thornhill, P.G., Conway, K., Miller, C., Patierno, S.R. & Costa, M. (1987). Physicochemical characteristics and biological effects of nickel oxides. Carcinogenesis 8(2):305-313.</ref><ref>IARC (2012). “Nickel and nickel compounds” ''IARC Monogr Eval Carcinog Risks Hum,'' Volume 100C: 169-218.'' '' (https://monographs.iarc.fr/ENG/Monographs/vol100C/mono100C-10.pdf ).</ref><ref>{{CELEX|32008R1272|text=Regulation (EC) No 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labelling and packaging of substances and mixtures, amending and repealing Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006}}</ref><ref>[https://www.unece.org/fileadmin/DAM/trans/danger/publi/ghs/ghs_rev05/English/ST-SG-AC10-30-REv5e.pdf Globally Harmonised System of Classification and Labelling of Chemicals (GHS), Fifth revised edition, United Nations, New York, and Geneva, 2013. PDF unece.org] Accessed July 13, 2017.</ref><ref>NTP (National Toxicology Program). 2016. “Report on Carcinogens”, 14th Edition.; Research Triangle Park, NC: U.S. Department of Health and Human Services, Public Health Service. https://ntp.niehs.nih.gov/pubhealth/roc/index-1.html Accessed July 13, 2017.</ref> based on increased respiratory cancer risks observed in epidemiological studies of sulfidic ore refinery workers.<ref>International Committee on Nickel Carcinogenesis in Man (ICNCM). (1990). Report of the International Committee on Nickel Carcinogenesis in Man. ''Scan. J. Work Environ. Health.'' '''16(1):''' 1-82.</ref>

In a 2-year National Toxicology Program green NiO inhalation study, some evidence of carcinogenicity in F344/N rats but equivocal evidence in female B6C3F1 mice was observed; there was no evidence of carcinogenicity in male B6C3F1 mice.<ref name=":1" /> Chronic inflammation without fibrosis was observed in the 2-year studies.

{{Reflist}}

{{Oxides}}

{{Authority control}}

[[Category:Transition metal oxides]]

[[Category:Hydrogenation catalysts]]

[[Category:Rock salt crystal structure]]