Lithium nitride

Last updated
Lithium nitride
Lithium-nitride-xtal-CM-3D-polyhedra.png
__ Li +     __ N3−
Structure Li3N.svg
Crystal structure of lithium nitride.
Names
Preferred IUPAC name
Lithium nitride
Other names
  • Trilithium azanide
  • Trilithium nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.043.144 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 247-475-2
1156
PubChem CID
  • InChI=1S/3Li.N
    Key: IDBFBDSKYCUNPW-UHFFFAOYSA-N
  • InChI=1S/3Li.N/q;;+1;-1
    Key: AJUFTLIHDBAQOK-UHFFFAOYSA-N
  • [Li]N([Li])[Li]
  • [Li+].[Li][N-][Li]
Properties
Li3N
Molar mass 34.83 g·mol−1
AppearanceRed-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
Occupational safety and health (OHS/OSH):
Main hazards
reacts with water to release ammonia
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-acid.svg
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)
NFPA 704.svgHealth (blue): no hazard codeFlammability 0: Will not burn. E.g. waterInstability 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
0
2
W
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).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Lithium nitride is an inorganic compound with the chemical formula Li 3 N . It is the only stable alkali metal nitride. It is a reddish-pink solid with a high melting point. [1]

Contents

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

Two other forms are known:

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]

Related Research Articles

<span class="mw-page-title-main">Alkali metal</span> Group of highly reactive chemical elements

The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and francium (Fr). Together with hydrogen they constitute group 1, which lies in the s-block of the periodic table. All alkali metals have their outermost electron in an s-orbital: this shared electron configuration results in their having very similar characteristic properties. Indeed, the alkali metals provide the best example of group trends in properties in the periodic table, with elements exhibiting well-characterised homologous behaviour. This family of elements is also known as the lithium family after its leading element.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

<span class="mw-page-title-main">Lithium aluminium hydride</span> Chemical compound

Lithium aluminium hydride, commonly abbreviated to LAH, is an inorganic compound with the chemical formula Li[AlH4] or LiAlH4. It is a white solid, discovered by Finholt, Bond and Schlesinger in 1947. This compound is used as a reducing agent in organic synthesis, especially for the reduction of esters, carboxylic acids, and amides. The solid is dangerously reactive toward water, releasing gaseous hydrogen (H2). Some related derivatives have been discussed for hydrogen storage.

<span class="mw-page-title-main">Stibine</span> Chemical compound

Stibine (IUPAC name: stibane) is a chemical compound with the formula SbH3. A pnictogen hydride, this colourless, highly toxic gas is the principal covalent hydride of antimony, and a heavy analogue of ammonia. The molecule is pyramidal with H–Sb–H angles of 91.7° and Sb–H distances of 170.7 pm (1.707 Å). This gas has an offensive smell like hydrogen sulfide (rotten eggs).

<span class="mw-page-title-main">Lithium hydride</span> Chemical compound

Lithium hydride is an inorganic compound with the formula LiH. This alkali metal hydride is a colorless solid, although commercial samples are grey. Characteristic of a salt-like (ionic) hydride, it has a high melting point, and it is not soluble but reactive with all protic organic solvents. It is soluble and nonreactive with certain molten salts such as lithium fluoride, lithium borohydride, and sodium hydride. With a molar mass of 7.95 g/mol, it is the lightest ionic compound.

<span class="mw-page-title-main">Ammonia borane</span> Chemical compound

Ammonia borane, also called borazane, is the chemical compound with the formula H3NBH3. The colourless or white solid is the simplest molecular boron-nitrogen-hydride compound. It has attracted attention as a source of hydrogen fuel, but is otherwise primarily of academic interest.

<span class="mw-page-title-main">Electride</span> Ionic compound with electrons as the anion

An electride is an ionic compound in which an electron serves the role of the anion. Solutions of alkali metals in ammonia are electride salts. In the case of sodium, these blue solutions consist of [Na(NH3)6]+ and solvated electrons:

A solvated electron is a free electron in a solution, in which it behaves like an anion. An electron's being solvated in a solution means it is bound by the solution. The notation for a solvated electron in formulas of chemical reactions is "e". Often, discussions of solvated electrons focus on their solutions in ammonia, which are stable for days, but solvated electrons also occur in water and many other solvents – in fact, in any solvent that mediates outer-sphere electron transfer. The solvated electron is responsible for a great deal of radiation chemistry.

<span class="mw-page-title-main">Zinc nitride</span> Chemical compound

Zinc nitride (Zn3N2) is an inorganic compound of zinc and nitrogen, usually obtained as (blue)grey crystals. It is a semiconductor. In pure form, it has the anti-bixbyite structure.

<span class="mw-page-title-main">Lithium aluminate</span> Chemical compound

Lithium aluminate, also called lithium aluminium oxide, is an inorganic chemical compound, an aluminate of lithium. In microelectronics, lithium aluminate is considered as a lattice matching substrate for gallium nitride. In nuclear technology, lithium aluminate is of interest as a solid tritium breeder material, for preparing tritium fuel for nuclear fusion. Lithium aluminate is a layered double hydroxide (LDH) with a crystal structure resembling that of hydrotalcite. Lithium aluminate solubility at high pH is much lower than that of aluminium oxides. In the conditioning of low- and intermediate level radioactive waste (LILW), lithium nitrate is sometimes used as additive to cement to minimise aluminium corrosion at high pH and subsequent hydrogen production. Indeed, upon addition of lithium nitrate to cement, a passive layer of LiH(AlO
2
)
2
· 5 H
2
O
is formed onto the surface of metallic aluminium waste immobilised in mortar. The lithium aluminate layer is insoluble in cement pore water and protects the underlying aluminium oxide covering the metallic aluminium from dissolution at high pH. It is also a pore filler. This hinders the aluminium oxidation by the protons of water and reduces the hydrogen evolution rate by a factor of 10.

<span class="mw-page-title-main">Lithium amide</span> Chemical compound

Lithium amide or lithium azanide is an inorganic compound with the chemical formula LiNH2. It is a white solid with a tetragonal crystal structure. Lithium amide can be made by treating lithium metal with liquid ammonia:

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

Lithium carbide, Li2C2, often known as dilithium acetylide, is a chemical compound of lithium and carbon, an acetylide. It is an intermediate compound produced during radiocarbon dating procedures. Li2C2 is one of an extensive range of lithium-carbon compounds which include the lithium-rich Li4C, Li6C2, Li8C3, Li6C3, Li4C3, Li4C5, and the graphite intercalation compounds LiC6, LiC12, and LiC18.

<span class="mw-page-title-main">Lithium imide</span> Chemical compound

Lithium imide is an inorganic compound with the chemical formula Li2NH. This white solid can be formed by a reaction between lithium amide and lithium hydride.

<span class="mw-page-title-main">NASICON</span> Class of solid materials

NASICON is an acronym for sodium (Na) super ionic conductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3−xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.

<span class="mw-page-title-main">Tetramethyldiborane</span> Chemical compound

Dimethylborane, (CH3)2BH is the simplest dialkylborane, consisting of a methyl group substituted for a hydrogen in borane. As for other boranes it normally exists in the form of a dimer called tetramethyldiborane or tetramethylbisborane or TMDB ((CH3)2BH)2. Other combinations of methylation occur on diborane, including monomethyldiborane, trimethyldiborane, 1,2-dimethylborane, 1,1-dimethylborane and trimethylborane. At room temperature the substance is at equilibrium between these forms. The methylboranes were first prepared by H. I. Schlesinger and A. O. Walker in the 1930s.

Lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12) or lithium lanthanum zirconate is a lithium-stuffed garnet material that is under investigation for its use in solid-state electrolytes in lithium-based battery technologies. LLZO has a high ionic conductivity and thermal and chemical stability against reactions with prospective electrode materials, mainly lithium metal, giving it an advantage for use as an electrolyte in solid-state batteries. LLZO exhibits favorable characteristics, including the accessibility of starting materials, cost-effectiveness, and straightforward preparation and densification processes. These attributes position this zirconium-containing lithium garnet as a promising solid electrolyte for all-solid-state lithium-ion rechargeable batteries.

<span class="mw-page-title-main">Abiological nitrogen fixation using homogeneous catalysts</span> Chemical process that converts nitrogen to ammonia

Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions.

<span class="mw-page-title-main">Nitrogen pentahydride</span> Chemical compound

Nitrogen pentahydride, also known as ammonium hydride is a hypothetical compound with the chemical formula NH5. There are two theoretical structures of nitrogen pentahydride. One structure is trigonal bipyramidal molecular geometry type NH5 molecule. Its nitrogen atom and hydrogen atoms are covalently bounded, and its symmetry group is D3h. Another predicted structure of nitrogen pentahydride is an ionic compound, composed of an ammonium ion and a hydride ion (NH4+H). Until now, no one has synthesized this substance, or proved its existence, and related experiments have not directly observed nitrogen pentahydride. It is only speculated that it may be a reactive intermediate based on reaction products. Theoretical calculations show this molecule is thermodynamically unstable. The reason might be similar to the instability of nitrogen pentafluoride, so the possibility of its existence is low. However, nitrogen pentahydride might exist in special conditions or high pressure. Nitrogen pentahydride was considered for use as a solid rocket fuel for research in 1966.

Neodymium(III) nitride is a chemical compound of neodymium and nitrogen with the formula NdN in which neodymium exhibits the +3 oxidation state and nitrogen exhibits the -3 oxidation state. It is ferromagnetic, like gadolinium(III) nitride, terbium(III) nitride and dysprosium(III) nitride. Neodymium(III) nitride is not usually stoichiometric, and it is very hard to create pure stoichiometric neodymium nitride.

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. 1 2 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. Bibcode:1976PhLA...58..231B. doi:10.1016/0375-9601(76)90082-7.
  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. 115 (42). The Journal of Physical Chemistry A 115 (42), 11678-11681: 11678–11681. Bibcode:2011JPCA..11511678H. doi:10.1021/jp205499e. PMID   21910502.
  9. Darren Quick (21 May 2012). "Chemical reaction eats up CO2 to produce energy...and other useful stuff". NewAtlas.com. Retrieved 17 April 2019.
  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. Bibcode:2002Natur.420..302C. doi:10.1038/nature01210. PMID   12447436. S2CID   95588150.

See also