Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and Sodium hydride: Difference between pages - Wikipedia

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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid [{{fullurl:Sodium_hydride|oldid=458300417}} 458300417] of page [[Sodium_hydride]] with values updated to verified values.}}

{{chembox

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 458298825464401664

| Name = Sodium hydride

| ImageFile = Sodium-hydride-3D-vdWNaH.pngjpg

| ImageSize = 200px

| ImageName = Sodium hydride

| ImageFile2 = Sodium-hydride-3D-vdW.png

| ImageName2 = Space-filling model of part of the crystal structure of sodium hydride

| ImageCaption2 = {{legend|rgb(160,84,224)|Sodium cation, {{chem2|Na+}}}}{{legend|white|Hydrogen anion, {{chem2|H−}}}}

|IUPACName=Sodium hydride

| Section1 = {{Chembox Identifiers

| InChI1 = 1S/Na.H/q+1;-1

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| CASNo = 7646-69-7

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

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

| UNII = 23J3BHR95O

| PubChem = 24758

| EINECS = 231-587-3

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| InChIKey = BZKBCQXYZZXSCO-UHFFFAOYAY

| StdInChI_Ref = {{stdinchicite|changed|chemspider}}

| StdInChI = 1S/Na.H/q+1;-1

| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}

| StdInChIKey = BZKBCQXYZZXSCOMPMYQQHEHYDOCL-UHFFFAOYSA-N}}

}}

| Section2 = {{Chembox Properties

| Formula = NaH

| MolarMass = 23.99771998 g/mol<ref name=crc>Haynes, p. 4.86</ref>

| Appearance = colorlesswhite toor grey solid

| Density = 1.39639 g/cm³<ref name=crc/>

| Solubility = reactsReacts with water<ref name=crc/>

| SolubleOther = insoluble in [[ammonia]],all [[benzene]],solvents [[carbon tetrachloride|CCl₄]], [[carbon disulfide|CS₂]]

| MeltingPtC = 638

| MeltingPt = 800 °C (decomposes)

| MeltingPt_ref = (decomposes)<ref name=crc/>

| RefractIndex = 1.470

| BandGap = 3.51 eV ''(predicted)''<ref>{{cite journal |last1=Singh |first1=S. |last2=Eijt |first2=S. W. H. |title=Hydrogen vacancies facilitate hydrogen transport kinetics in sodium hydride nanocrystallites |journal=Physical Review B |date=30 December 2008 |volume=78 |issue=22 |pages=224110 |doi=10.1103/PhysRevB.78.224110|bibcode=2008PhRvB..78v4110S |url=http://resolver.tudelft.nl/uuid:3632cb10-4454-49ab-91c4-6df5dfcfd5b4 }}</ref>

}}

| RefractIndex = 1.470<ref>{{cite book|last1=Batsanov|first1=Stepan S.|last2=Ruchkin|first2=Evgeny D.|last3=Poroshina|first3=Inga A.|title=Refractive Indices of Solids|url=https://books.google.com/books?id=yF_SDAAAQBAJ&pg=PA35|date= 2016|publisher=Springer|isbn=978-981-10-0797-2|page=35}}</ref>}}

| Section3 = {{Chembox Structure

| CrystalStruct = [[Cubic crystal system|fcc]] ([[Sodium chloride#Crystal structure|NaCl]]), [[Pearson symbol|cF8]]

| SpaceGroup = Fm{{overline|3}}m, No. 225

| Coordination = Octahedral (Na⁺)<br/>Octahedral (H^–−)

| LattConst_a = 498 pm

| UnitCellFormulas = 4}}

}}

| Section4 = {{Chembox Thermochemistry

|Thermochemistry_ref=<ref>Haynes, p. 5.35</ref><ref name=b1>{{cite book| author = Zumdahl, Steven S.|title =Chemical Principles 6th Ed.| publisher = Houghton Mifflin Company| year = 2009| isbn = 978-0-618-94690-7|page=A23}}</ref>

| DeltaHf = −56.3 kJ·mol⁻¹

| DeltaGf = -33.5 kJ/mol

| Entropy = 40.0 J·mol⁻¹·K⁻¹<ref name=b1/>

| HeatCapacity = 36.4 J/mol K}}

| Section7 = {{Chembox Hazards

| ExternalMSDSExternalSDS = [https://fscimage.fishersci.com/msds/99406.htm External MSDS]

| Reference GHS_ref= <ref>{{CLP Regulation|index=001-002-00-4|page=340}}</ref>

| GHSPictograms = {{GHS02GHS flame|Water-react. 1}}▼

| EUIndex = 001-003-00-X

▲| GHSPictograms = {{GHS02|Water-react. 1}}

| GHSSignalWord = DANGER

| HPhrases = {{H-phrases|260}}

| MainHazards = highly corrosive, reacts violently with water or humid air.

| NFPA-H = 3

| NFPA-F = 13

| NFPA-R = 02

| NFPA-OS = W

| FlashPt = combustible}}<ref>{{cite web |url=https://www.newenv.com/resources/nfpa_chemicals |title=New Environment Inc. – NFPA Chemicals |website=newenv.com |url-status=live |archive-url=https://web.archive.org/web/20160827183112/https://www.newenv.com/resources/nfpa_chemicals/ |archive-date=2016-08-27}}</ref>

| RPhrases =

| SPhrases =

| FlashPt = combustible

}}

| Section8 = {{Chembox Related

| OtherCations = [[Lithium hydride]]<br/>[[Potassium hydride]]<br>[[Rubidium hydride]]<br>[[Caesium hydride]]

| OtherCpdsOtherAnions = [[Sodium borohydride]]<br>[[Sodium hydroxide]]}}}}

'''Sodium hydride''' is the [[chemical compound]] with the [[empirical formula]] [[sodium|Na]][[hydrogen|H]]. This [[alkali metal hydride]] is primarily used as a strong yet combustible [[base (chemistry)|base]] in [[organic synthesis]]. NaH is a saline (salt-like) [[hydride]], composed of Na⁺ and H⁻ ions, in contrast to molecular hydrides such as [[borane]], [[silane]], [[germane]], [[ammonia]], and [[methane]]. It is an ionic material that is insoluble in all solvents (other than molten sodium metal), consistent with the fact that H⁻ ions do not exist in solution.

}}

}}

==Basic properties and structure==

NaH is colorless, although samples generally appear grey. NaH is around 40% denser than Na (0.968 g/cm³).

NaH, like [[lithium hydride|LiH]], [[potassium hydride|KH]], [[rubidium hydride|RbH]], and [[caesium hydride|CsH]], adopts the [[sodium chloride|NaCl]] [[crystal structure]]. In this motif, each Na⁺ ion is surrounded by six H⁻ centers in an [[octahedral molecular geometry|octahedral]] geometry. The [[ionic radius|ionic radii]] of H⁻ (146 pm in NaH) and F⁻ (133 pm) are comparable, as judged by the Na−H and Na−F distances.<ref>Wells, A.F. (1984). ''Structural Inorganic Chemistry'', Oxford: Clarendon Press</ref>

==="Inverse sodium hydride" (hydrogen sodide) ===

A very unusual situation occurs in a compound dubbed "inverse sodium hydride", which contains H⁺ and Na⁻ ions. Na⁻ is an [[alkalide]], and this compound differs from ordinary sodium hydride in having a much higher energy content due to the net displacement of two electrons from hydrogen to sodium. A derivative of this "inverse sodium hydride" arises in the presence of the base [[adamanzane|[3⁶]adamanzane]]. This molecule irreversibly encapsulates the H⁺ and shields it from interaction with the alkalide Na⁻.<ref>{{cite journal |title="Inverse Sodium Hydride": A Crystalline Salt that Contains H⁺ and Na⁻ |journal=J. Am. Chem. Soc. |year=2002 |volume=124 |issue=21 |pages=5928–5929 |doi=10.1021/ja025655+ |pmid=12022811 |last1=Redko |first1=M. Y. |last2=Vlassa |first2=M. |last3=Jackson |first3=J. E. |last4=Misiolek |first4=A. W. |last5=Huang |first5=R. H. |last6=Dye |first6=J. L. |display-authors=etal}}</ref> Theoretical work has suggested that even an unprotected protonated tertiary amine complexed with the sodium alkalide might be metastable under certain solvent conditions, though the barrier to reaction would be small and finding a suitable solvent might be difficult.<ref>{{cite journal |url=http://simons.hec.utah.edu/papers/266.pdf |title=Inverse Sodium Hydride: A Theoretical Study |journal=J. Am. Chem. Soc. |year=2003 |volume=125 |pages=3954–3958 |doi=10.1021/ja021136v |pmid=12656631 |issue=13 |last1=Sawicka |first1=Agnieszka |last2=Skurski |first2=Piotr |last3=Simons |first3=Jack |url-status=live |archive-url=https://web.archive.org/web/20130209002911/http://simons.hec.utah.edu/papers/266.pdf |archive-date=2013-02-09}}</ref>

== Preparation ==

Industrially, NaH is prepared by introducing molten sodium into mineral oil with hydrogen at atmospheric pressure and mixed vigorously at ~8000 rpm. The reaction is especially rapid at 250−300 °C.

:{{chem2|2 Na + H2 → 2 NaH}}

The resultant suspension of NaH in mineral oil is often directly used, such as in the production of [[diborane]].<ref>{{Citation |last1=Rittmeyer |first1=Peter |title=Hydrides |date=2000-06-15 |url=https://onlinelibrary.wiley.com/doi/10.1002/14356007.a13_199 |encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry |editor-last=Wiley-VCH Verlag GmbH & Co. KGaA |access-date=2023-11-21 |place=Weinheim, Germany |publisher=Wiley-VCH Verlag GmbH & Co. KGaA |language=en |doi=10.1002/14356007.a13_199 |isbn=978-3-527-30673-2 |last2=Wietelmann |first2=Ulrich}}</ref>

==Applications in organic synthesis==

===As a strong base===

NaH is a base of wide scope and utility in organic chemistry.<ref>''Encyclopedia of Reagents for Organic Synthesis'' (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. {{doi|10.1002/047084289X}}.</ref> As a [[superbase]], it is capable of [[deprotonating]] a range of even weak [[Brønsted acid]]s to give the corresponding sodium derivatives. Typical "easy" substrates contain O-H, N-H, S-H bonds, including [[Alcohol (chemistry)|alcohol]]s, [[phenol]]s, [[pyrazole]]s, and [[thiol]]s.

NaH notably deprotonates carbon acids (i.e., C-H bonds) such as 1,3-[[dicarbonyl]]s such as [[malonic ester]]s. The resulting sodium derivatives can be alkylated. NaH is widely used to promote condensation reactions of carbonyl compounds via the [[Dieckmann condensation]], [[Stobbe condensation]], [[Darzens condensation]], and [[Claisen condensation]]. Other carbon acids susceptible to deprotonation by NaH include sulfonium salts and [[dimethyl sulfoxide|DMSO]]. NaH is used to make [[sulfur]] [[ylide]]s, which in turn are used to convert [[ketone]]s into [[epoxide]]s, as in the [[Johnson–Corey–Chaykovsky reaction]].

===As a reducing agent===

NaH reduces certain main group compounds, but analogous reactivity is very rare in organic chemistry (''see below'').<ref>{{cite journal|last1=Too|first1=Pei Chui|last2=Chan|first2=Guo Hao|last3=Tnay|first3=Ya Lin|last4=Hirao|first4=Hajime|last5=Chiba|first5=Shunsuke|date=2016-03-07|title=Hydride Reduction by a Sodium Hydride–Iodide Composite|journal=Angewandte Chemie International Edition|language=en|volume=55|issue=11|pages=3719–3723|doi=10.1002/anie.201600305|issn=1521-3773|pmc=4797714|pmid=26878823}}<br>For early examples of NaH acting as a hydride donor, see ref. [3] therein.{{citation needed|date=September 2021}}</ref> Notably [[boron trifluoride]] reacts to give [[diborane]] and [[sodium fluoride]]:<ref name="Holl">Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. {{ISBN|0-12-352651-5}}.</ref>

:6 NaH + 2 BF₃ → B₂H₆ + 6 NaF

Si–Si and S–S bonds in [[disilane]]s and [[disulfide]]s are also reduced.

A series of reduction reactions, including the hydrodecyanation of tertiary nitriles, reduction of imines to amines, and amides to aldehydes, can be effected by a composite reagent composed of sodium hydride and an alkali metal iodide (NaH⋅MI, M = Li, Na).<ref>{{cite journal|last1=Ong|first1=Derek Yiren|last2=Tejo|first2=Ciputra|last3=Xu|first3=Kai|last4=Hirao|first4=Hajime|last5=Chiba|first5=Shunsuke|date=2017-01-01|title=Hydrodehalogenation of Haloarenes by a Sodium Hydride–Iodide Composite|journal=Angewandte Chemie International Edition|volume=56|issue=7|language=en|pages=1840–1844|doi=10.1002/anie.201611495|pmid=28071853|hdl=10356/154861 |issn=1521-3773|hdl-access=free}}</ref>

===Hydrogen storage===

Although not commercially significant sodium hydride has been proposed for hydrogen storage for use in [[fuel cell]] vehicles. In one experimental implementation, plastic pellets containing NaH are crushed in the presence of water to release the hydrogen. One challenge with this technology is the regeneration of NaH from the NaOH formed by hydrolysis.<ref>{{cite web |url= https://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/28890pp2.pdf |title= Analysis of the Sodium Hydride-based Hydrogen Storage System being developed by PowerBall Technologies, LLC |author= DiPietro, J. Philip |author2= Skolnik, Edward G. |date= October 1999 |publisher= US Department of Energy, Office of Power Technologies |access-date= 2009-09-01 |url-status= live |archive-url= https://web.archive.org/web/20061213093231/http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/28890pp2.pdf |archive-date= 2006-12-13}}</ref>

==Practical considerations==

Sodium hydride is sold as a mixture of 60% sodium hydride (w/w) in [[mineral oil]]. Such a dispersion is safer to handle and weigh than pure NaH. The compound is often used in this form but the pure grey solid can be prepared by rinsing the commercial product with pentane or tetrahydrofuran, with care being taken because the waste solvent will contain traces of NaH and can ignite in air. Reactions involving NaH usually require [[air-free technique]]s.

==Safety==

NaH can [[pyrophoricity|ignite spontaneously in air]]. It also reacts vigorously with water or humid air to release [[hydrogen]], which is very flammable, and [[sodium hydroxide]] (NaOH), a quite corrosive [[base (chemistry)|base]]. In practice, most sodium hydride is sold as a dispersion in [[mineral oil]], which can be safely handled in air.<ref>{{cite web|url=http://www.rohmhaas.com/wcm/products/product_detail.page?display-mode=msds&product=1120734&application=1120208|title=The Dow Chemical Company – Home|website=www.rohmhaas.com}}</ref> Although sodium hydride is widely used in [[Dimethylsulfoxide|DMSO]], [[Dimethylformamide|DMF]] or [[Dimethylacetamide|DMAc]] for [[SN2 Reaction|SN2 type reactions]] there have been many cases of fires and/or explosions from such mixtures.<ref>{{cite journal |doi=10.1021/acs.oprd.9b00276 |doi-access=free |title=Explosion Hazards of Sodium Hydride in Dimethyl Sulfoxide, N,N-Dimethylformamide, and N,N-Dimethylacetamide |year=2019 |last1=Yang |first1=Qiang |last2=Sheng |first2=Min |last3=Henkelis |first3=James J. |last4=Tu |first4=Siyu |last5=Wiensch |first5=Eric |last6=Zhang |first6=Honglu |last7=Zhang |first7=Yiqun |last8=Tucker |first8=Craig |last9=Ejeh |first9=David E. |journal=Organic Process Research & Development |volume=23 |issue=10 |pages=2210–2217 }}</ref><ref>[http://www.crhf.org.uk/incident101.html UK Chemical Reaction Hazards Forum] {{Webarchive|url=https://web.archive.org/web/20111006011739/http://www.crhf.org.uk/incident101.html |date=2011-10-06}} and references cited therein</ref>

==References==

{{Reflist}}

==Cited sources==

*{{cite book | editor= Haynes, William M. | date = 2016| title = [[CRC Handbook of Chemistry and Physics]] | edition = 97th | publisher = [[CRC Press]] | isbn = 9781498754293}}

{{Sodium compounds}}

{{Hydrides by group}}

[[Category:Metal hydrides]]

[[Category:Reagents for organic chemistry]]

[[Category:Sodium compounds]]

[[Category:Superbases]]

[[Category:Rock salt crystal structure]]

[[Category:Semiconductor materials]]