Lithium nitride
__ Li+ __ N3− | |
Crystal structure of lithium nitride. | |
Names | |
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Preferred IUPAC name Lithium nitride | |
Other names
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Identifiers | |
CAS Number |
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3D model (JSmol) |
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ChEBI |
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ChemSpider |
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ECHA InfoCard | 100.043.144 |
EC Number |
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Gmelin Reference | 1156 |
PubChem CID |
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CompTox Dashboard (EPA) |
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InChI
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Properties | |
Chemical formula | Li3N |
Molar mass | 34.83 g·mol−1 |
Appearance | Red-purple or reddish-pink crystals or powder |
Density | 1.270 g/cm3 |
Melting point | 813 °C (1,495 °F; 1,086 K) |
Solubility in water | reacts |
log P | 3.24 |
Structure | |
Crystal structure | see text |
Hazards | |
Occupational safety and health (OHS/OSH): | |
Main hazards | reacts with water to release ammonia |
GHS labelling: | |
Pictograms | |
Danger | |
H260, H314 | |
P223, P231+P232, P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P335+P334, P363, P370+P378, P402+P404, P405, P501 | |
NFPA 704 (fire diamond) | 0 2 W |
Related compounds | |
Other anions | |
Other cations |
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Related compounds | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references |
Lithium nitride is an inorganic compound with the chemical formula Li3N. It is the only stable alkali metal nitride. It is a reddish-pink solid with a high melting point.[1]
Preparation and handling
Lithium nitride is prepared by direct reaction of elemental lithium with nitrogen gas:[2]
- 6 Li + N2 → 2 Li3N
Instead of burning lithium metal in an atmosphere of nitrogen, a solution of lithium in liquid sodium metal can be treated with N2.
Lithium nitride must be protected from moisture as it reacts violently with water to produce ammonia:
- Li3N + 3 H2O → 3 LiOH + NH3
Structure and properties
- alpha-Li3N (stable at room temperature and pressure) has an unusual crystal structure that consists of two types of layers: one layer has the composition Li2N− contains 6-coordinate N centers and the other layer consists only of lithium cations.[3]
Two other forms are known:
- beta-Li3N, formed from the alpha phase at 0.42 GPa has the sodium arsenide (Na3As) structure;
- gamma-Li3N (same structure as lithium bismuthide Li3Bi) forms from the beta form at 35 to 45 GPa.[4]
Lithium nitride shows ionic conductivity for Li+, with a value of c. 2×10−4 Ω−1cm−1, and an (intracrystal) activation energy of c. 0.26 eV (c. 24 kJ/mol). Hydrogen doping increases conductivity, whilst doping with metal ions (Al, Cu, Mg) reduces it.[5][6] The activation energy for lithium transfer across lithium nitride crystals (intercrystalline) has been determined to be higher, at c. 68.5 kJ/mol.[7] The alpha form is a semiconductor with band gap of c. 2.1 eV.[4]
Reactions
Reacting lithium nitride with carbon dioxide results in amorphous carbon nitride (C3N4), a semiconductor, and lithium cyanamide (Li2CN2), a precursor to fertilizers, in an exothermic reaction.[8][9]
Under hydrogen at around 200°C, Li3N will react to form lithium amide.[10]
- Li3N + 2 H2 → 2LiH + 2LiNH2
At higher temperatures it will react further to form ammonia and lithium hydride.
- LiNH2 + H2 → LiH + NH3
Lithium imide can also be formed under certain conditions. Some research has explored this as a possible industrial process to produce ammonia since lithium hydride can be thermally decomposed back to lithium metal.
Lithium nitride has been investigated as a storage medium for hydrogen gas, as the reaction is reversible at 270 °C. Up to 11.5% by weight absorption of hydrogen has been achieved.[11]
References
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
- ^ E. Döneges "Lithium Nitride" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, New York. Vol. 1. p. 984.
- ^ Barker M. G.; Blake A. J.; Edwards P. P.; Gregory D. H.; Hamor T. A.; Siddons D. J.; Smith S. E. (1999). "Novel layered lithium nitridonickelates; effect of Li vacancy concentration on N co-ordination geometry and Ni oxidation state". Chemical Communications (13): 1187–1188. doi:10.1039/a902962a.
- ^ a b Walker, G, ed. (2008). Solid-State Hydrogen Storage: Materials and Chemistry. §16.2.1 Lithium nitride and hydrogen:a historical perspective.
- ^ Lapp, Torben; Skaarup, Steen; Hooper, Alan (October 1983). "Ionic conductivity of pure and doped Li3N". Solid State Ionics. 11 (2): 97–103. doi:10.1016/0167-2738(83)90045-0.
- ^ Boukamp, B. A.; Huggins, R. A. (6 September 1976). "Lithium ion conductivity in lithium nitride". Physics Letters A. 58 (4): 231–233. Bibcode:1976PhLA...58..231B. doi:10.1016/0375-9601(76)90082-7.
- ^ Boukamp, B. A.; Huggins, R. A. (January 1978). "Fast ionic conductivity in lithium nitride". Materials Research Bulletin. 13 (1): 23–32. doi:10.1016/0025-5408(78)90023-5.
- ^ Yun Hang Hu, Yan Huo (12 September 2011). "Fast and Exothermic Reaction of CO2 and Li3N into C–N-Containing Solid Materials". The Journal of Physical Chemistry A. 115 (42). The Journal of Physical Chemistry A 115 (42), 11678-11681: 11678–11681. Bibcode:2011JPCA..11511678H. doi:10.1021/jp205499e. PMID 21910502.
- ^ Darren Quick (21 May 2012). "Chemical reaction eats up CO2 to produce energy...and other useful stuff". NewAtlas.com. Retrieved 17 April 2019.
- ^ Goshome, Kiyotaka; Miyaoka, Hiroki; Yamamoto, Hikaru; Ichikawa, Tomoyuki; Ichikawa, Takayuki; Kojima, Yoshitsugu (2015). "Ammonia Synthesis via Non-Equilibrium Reaction of Lithium Nitride in Hydrogen Flow Condition". Materials Transactions. 56 (3): 410–414. doi:10.2320/matertrans.M2014382.
- ^ Ping Chen; Zhitao Xiong; Jizhong Luo; Jianyi Lin; Kuang Lee Tan (2002). "Interaction of hydrogen with metal nitrides and amides". Nature. 420 (6913): 302–304. Bibcode:2002Natur.420..302C. doi:10.1038/nature01210. PMID 12447436. S2CID 95588150.
See also
- WebElements
- v
- t
- e
- Li2
- LiAlCl4
- Li1+xAlxGe2−x(PO4)3
- LiAlH4
- LiAlO2
- LiAl1+xTi2−x(PO4)3
- LiAs
- LiAsF6
- Li3AsO4
- LiAt
- Li[AuCl4]
- LiB(C2O4)2
- LiB(C6F5)4
- LiWF6
- LiBF4
- LiBH4
- LiBO2
- LiB3O5
- Li2B4O7
- LiAsF6
- Li2SnF6
- Li2TiF6
- Li2ZrF6
- Li2B4O7·5H2O
- LiBSi2
- LiBr
- LiBr·2H2O
- LiBrO
- LiBrO2
- LiBrO3
- LiBrO4
- Li2C2
- LiCF3SO3
- CH3CH(OH)COOLi
- LiC2H2ClO2
- LiC2H3IO2
- Li(CH3)2N
- LiCHO2
- LiCH3O
- LiC2H5O
- LiCN
- Li2CN2
- LiCNO
- Li2CO3
- Li2C2O4
- LiCl
- LiCl·H2O
- LiClO
- LiFO
- LiClO2
- LiClO3
- LiClO4
- LiCoO2
- Li2CrO4
- Li2CrO4·2H2O
- Li2Cr2O7
- CsLiB6O10
- LiD
- LiF
- Li2F
- LiF4Al
- Li3F6Al
- FLiBe
- LiFePO4
- FLiNaK
- LiGaH4
- Li2GeF6
- Li2GeO3
- LiGe2(PO4)3
- LiH
- LiH2AsO4
- Li2HAsO4
- LiHCO3
- Li3H(CO3)2
- LiH2PO3
- LiH2PO4
- LiHSO3
- LiHSO4
- LiHe
- LiI
- LiIO
- LiIO2
- LiIO3
- LiIO4
- Li2IrO3
- Li7La3Zr2O12
- LiMn2O4
- Li2MoO4
- Li0.9Mo6O17
- LiN3
- Li3N
- LiNH2
- Li2NH
- LiNO2
- LiNO3
- LiNO3·H2O
- Li2N2O2
- LiNa
- Li2NaPO3
- LiNaNO2
- LiNbO3
- Li2NbO3
- LiO−
- LiO2
- LiO3
- Li2O
- Li2O2
- LiOH
- Li3P
- LiPF6
- Li3PO4
- Li2HPO3
- Li2HPO4
- Li3PO3
- Li3PO4
- Li2Po
- Li2PtO3
- Li2RuO3
- Li2S
- LiSCN
- LiSH
- LiSO3F
- Li2SO3
- Li2SO4
- Li[SbF6]
- Li2Se
- Li2SeO3
- Li2SeO4
- LiSi
- Li2SiF6
- Li4SiO4
- Li2SiO3
- Li2Si2O5
- LiTaO3
- Li2Te
- LiTe3
- Li2TeO3
- Li2TeO4
- Li2TiO3
- Li4Ti5O12
- LiTi2(PO4)3
- LiVO3·2H2O
- Li3V2(PO4)3
- Li2WO4
- LiYF4
- LiZr2(PO4)3
- Li2ZrO3
- Hemolithin (extraterrestrial protein)
- Organolithium reagents
- CH3COOLi
- C4H6LiNO4
- LiC2F6NO4S2
- LiN(SiMe3)2
- Li3C6H5O7
- C5H5Li
- LiN(C3H7)2
- (C6H5)2PLi
- C18H35LiO3
- C6H13Li
- C4H9Li
- CH3CHLiCH2CH3
- (CH3)3CLi
- C12H28BLi
- CH3Li
- Li+C10H8−
- C5H11Li
- C5H3LiN2O4
- C6H5Li
- LiC2CH3
- LiO2C(CH2)16CH3
- C4H5LiO4
- LiEt3BH
- LiOC(CH3)3
- C9H18LiN
- LiC2H3 Vinyllithium
- LiC
11H
23COO
- Amblygonite
- Berezanskite
- Brannockite
- Cryolithionite
- Darapiosite
- Darrellhenryite
- Elbaite
- Fluorine Elbaite
- Fluor-liddicoatite
- Emeleusite
- Eucryptite LiAlSiO4
- Faizievite
- Hectorite
- Hsianghualite
- Jadarite LiNaSiB3O7OH
- Keatite Li(AlSi2O6)
- Kunzite
- Lavinskyite
- Lepidolite
- Lithiophilite LiMnPO4
- Lithiophosphate Li3PO4
- Manandonite
- Manganoneptunite
- Nambulite
- Neptunite
- Olympite
- Petalite LiAlSi4010
- Pezzottaite Cs(Be2Li)Al2Si6O18
- Rossmanite
- Saliotite
- Sogdianite
- Spodumene LiAl(SiO3)2
- Sugilite
- Tiptopite
- Tourmaline
- Triphylite LiFePO4
- Zabuyelite Li2CO3
- Zektzerite
- Zinnwaldite
- LixBey
- HLiHe+
- LiFHeO
- LiHe2
- (HeO)(LiF)2
- La2/3-xLi3xTiO3He
- Aluminium–lithium alloys
- Heteroatom-promoted lateral lithiation
- LB buffer
- Lithium atom
- Lithium medication
- LiNixCoyAlzO2
- LiNixMnyCozO2
- Lithium soap
- Lithium Triangle
- Lucifer yellow
- Magnesium–lithium alloys
- NASICON
- Environmentally friendly red light flare