Chemistry:Lithium nitride

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Lithium nitride
Unit cell ball and stick model of lithium nitride
__ Li+
     __ N3−
Names
Preferred IUPAC name
Lithium nitride
Other names
  • Trilithium azanide
  • Trilithium nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
EC Number
  • 247-475-2
1156
Properties
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)
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)
NFPA 704 four-colored diamondFlammability code 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity 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 acid
4
3
2
Related compounds
Other anions
Other cations
Related compounds
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 an inorganic compound with the chemical formula Li
3N. 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 + N
2 → 2 Li
3N

Instead of burning lithium metal in an atmosphere of nitrogen, a solution of lithium in liquid sodium metal can be treated with N
2.

Lithium nitride is an extremely strong base, so it must be protected from moisture as it reacts violently with water to produce ammonia:

Li
3N + 3 H
2O → 3 LiOH + NH
3

Structure and properties

  • alpha-Li
    3    N     (stable at room temperature and pressure) has an unusual crystal structure that consists of two types of layers: one layer has the composition Li
    2    N−
     contains 6-coordinate N centers and the other layer consists only of lithium cations.[3]

Two other forms are known:

  • beta-Li
    3    N    , formed from the alpha phase at 0.42 GPa has the sodium arsenide (Na
    3    As    ) structure;
  • gamma-Li
    3    N     (same structure as lithium bismuthide Li
    3    Bi    ) 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 (C
3N
4), a semiconductor, and lithium cyanamide (Li
2CN
2), a precursor to fertilizers, in an exothermic reaction.[8][9]

Under hydrogen at around 200°C, Li3N will react to form lithium amide.[10]

Li
3N + 2 H
2 → 2LiH + LiNH
2

At higher temperatures it will react further to form ammonia and lithium hydride.

LiNH
2 + H
2 → LiH + NH
3

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

  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. ↑ 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. 
  9. ↑ 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/. 
  10. ↑ 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. 
  11. ↑ 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. 

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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