Chemistry:Lithium nitride

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Lithium nitride
Unit cell ball and stick model of lithium nitride
__ Li+     __ N3−
Structure Li3N.svg
Crystal structure of lithium nitride.
Names
Preferred IUPAC name
Lithium nitride
Other names
Trilithium nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
EC Number
  • 247-475-2
1156
Properties
Li3N
Molar mass 34.83 g/mol
Appearance red, purple solid
Density 1.270 g/cm3
Melting point 813 °C (1,495 °F; 1,086 K)
reacts
log P 3.24
Structure
see text
Hazards
Main hazards reacts with water to release ammonia
GHS pictograms GHS02: FlammableGHS05: Corrosive
GHS Signal word Danger
H260, H314
P223, P231+232, P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P335+334, P363, P370+378, P402+404, P405, P501
NFPA 704 (fire diamond)
Flammability code 0: Will not burn. E.g. waterHealth (blue): no hazard codeReactivity code 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acidNFPA 704 four-colored diamond
0
2
Related compounds
Other anions
 Lithium oxide
Other cations
 Sodium nitride
Potassium nitride
Related compounds
 Lithium amide
Lithium imide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
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Lithium nitride is a compound with the formula Li3N. It is the only stable alkali metal nitride. The solid has a reddish-pink color and high melting point.[1]

Preparation and handling

Lithium nitride is prepared by direct combination 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 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 sheet has the composition Li2N− contains 6-coordinate N centers and the other sheet consists only of lithium cations.[3] Two other forms are known: beta-Lithium nitride, formed from the alpha phase at 4,200 bars (4,100 atm) has the sodium arsenide (Na3As) structure; gamma-Lithium nitride (same structure as Li3Bi) forms from the beta form at 35 to 45 gigapascals (350,000 to 440,000 atm).[4]

Lithium nitride shows ionic conductivity for Li+, with a value of c. 2×10−4Ω−1cm−1, and an (intracrystal) activation energy of c. 0.26eV (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]

Reaction with hydrogen at under 300 °C (0.5 MPa pressure) produces lithium hydride and lithium amide.[8]

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.[9]

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.[10] [11]

References

  1. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. 
  2. ↑ 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.
  3. ↑ 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. 
  4. ↑ 4.0 4.1 Walker, G, ed (2008). Solid-State Hydrogen Storage: Materials and Chemistry. §16.2.1 Lithium nitride and hydrogen:a historical perspective. 
  5. ↑ 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. 
  6. ↑ Boukamp, B. A.; Huggins, R. A. (6 September 1976). "Lithium ion conductivity in lithium nitride". Physics Letters A 58 (4): 231–233. doi:10.1016/0375-9601(76)90082-7. Bibcode: 1976PhLA...58..231B. 
  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. 
  8. ↑ 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. 
  9. ↑ 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. doi:10.1038/nature01210. PMID 12447436. Bibcode: 2002Natur.420..302C. 
  10. ↑ 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 (The Journal of Physical Chemistry A 115 (42), 11678-11681) 115 (42): 11678–11681. doi:10.1021/jp205499e. PMID 21910502. Bibcode: 2011JPCA..11511678H. 
  11. ↑ Darren Quick (21 May 2012). "Chemical reaction eats up CO2 to produce energy...and other useful stuff". NewAtlas.com. https://newatlas.com/co2-li3n-reaction/22620/. 

See also

Salts and covalent derivatives of the nitride ion
NH3 He(N2)11
Li3N Be3N2 BN β-C3N4
g-C3N4 		N2 NxOy NF3 Ne
Na3N Mg3N2 AlN Si3N4 PN
P3N5 		SxNy
SN
S4N4 		NCl3 Ar
K3N Ca3N2 ScN TiN VN CrN
Cr2N 		MnxNy FexNy CoN Ni3N CuN Zn3N2 GaN Ge3N4 As Se NBr3 Kr
Rb3N Sr3N2 YN ZrN NbN β-Mo2N Tc Ru Rh PdN Ag3N CdN InN Sn Sb Te NI3 Xe
Cs3N Ba3N2   Hf3N4 TaN WN Re Os Ir Pt Au Hg3N2 TlN Pb BiN Po At Rn
Fr3N Ra3N   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
La CeN Pr Nd Pm Sm Eu GdN Tb Dy Ho Er Tm Yb Lu
Ac Th Pa UN Np Pu Am Cm Bk Cf Es Fm Md No Lr




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