Magnesium nitride

Magnesium nitride, which possesses the chemical formula Mg3N2, is an inorganic compound of magnesium and nitrogen. At room temperature and pressure it is a greenish yellow powder.

Magnesium nitride
Names
IUPAC name
Magnesium nitride
Identifiers
ECHA InfoCard 100.031.826
UNII
Properties
Mg3N2
Molar mass 100.9494 g/mol
Appearance greenish yellow powder
Density 2.712 g/cm3
Melting point approx. 1500°C
Hazards
Safety data sheet External MSDS
R-phrases (outdated) R36, R37, R38
S-phrases (outdated) S26, S36
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

Preparation

  • By passing dry nitrogen over heated magnesium:
  • or ammonia:

Chemistry

Magnesium nitride reacts with water to produce magnesium hydroxide and ammonia gas, as do many metal nitrides.

Mg3N2(s) + 6 H2O(l) → 3 Mg(OH)2(aq) + 2 NH3(g)

In fact, when magnesium is burned in air, some magnesium nitride is formed in addition to the principal product, magnesium oxide.

Thermal decomposition of magnesium nitride gives magnesium and nitrogen gas (at 700-1500 °C).

At high pressures, the stability and formation of new nitrogen-rich nitrides (N/Mg ratio equal or greater to one) were suggested and later discovered.[1][2][3] These include the Mg2N4 and MgN4 solids which both become thermodynamically stable near 50 GPa.[4] The Mg2N4 is composed of exotic cis-tetranitrogen N44− species with N-N bond orders close to one. This Mg2N4 compound was recovered to ambient conditions, along with the N44− units, marking only the fourth polynitrogen entitiy bulk stabilized at ambient conditions.

Uses

Magnesium nitride was the catalyst in the first practical synthesis of borazon (cubic boron nitride).[5]

Robert H. Wentorf, Jr. was trying to convert the hexagonal form of boron nitride into the cubic form by a combination of heat, pressure, and a catalyst. He had already tried all the logical catalysts (for instance, those that catalyze the synthesis of diamond), but with no success.

Out of desperation and curiosity (he called it the "make the maximum number of mistakes" approach[6]), he added some magnesium wire to the hexagonal boron nitride and gave it the same pressure and heat treatment. When he examined the wire under a microscope, he found tiny dark lumps clinging to it. These lumps could scratch a polished block of boron carbide, something only diamond was known to do.

From the smell of ammonia, caused by the reaction of magnesium nitride with the moisture in the air, he deduced that the magnesium metal had reacted with the boron nitride to form magnesium nitride, which was the true catalyst.

When isolating argon, William Ramsay passed dry air over copper to remove oxygen and over magnesium to remove the nitrogen, forming magnesium nitride.

References

  1. Yu, Shuyin; Huang, Bowen; Zeng, Qingfeng; Oganov, Artem R.; Zhang, Litong; Frapper, Gilles (June 2017). "Emergence of Novel Polynitrogen Molecule-like Species, Covalent Chains, and Layers in Magnesium–Nitrogen Mg x N y Phases under High Pressure". The Journal of Physical Chemistry C. 121 (21): 11037–11046. doi:10.1021/acs.jpcc.7b00474. ISSN 1932-7447.
  2. Wei, Shuli; Li, Da; Liu, Zhao; Li, Xin; Tian, Fubo; Duan, Defang; Liu, Bingbing; Cui, Tian (2017). "Alkaline-earth metal (Mg) polynitrides at high pressure as possible high-energy materials". Physical Chemistry Chemical Physics. 19 (13): 9246–9252. doi:10.1039/C6CP08771J. ISSN 1463-9076. PMID 28322368.
  3. Xia, Kang; Zheng, Xianxu; Yuan, Jianan; Liu, Cong; Gao, Hao; Wu, Qiang; Sun, Jian (2019-04-25). "Pressure-Stabilized High-Energy-Density Alkaline-Earth-Metal Pentazolate Salts". The Journal of Physical Chemistry C. 123 (16): 10205–10211. doi:10.1021/acs.jpcc.8b12527. ISSN 1932-7447.
  4. Laniel, Dominique; Winkler, Bjoern; Koemets, Egor; Fedotenko, Timofey; Bykov, Maxim; Bykova, Elena; Dubrovinsky, Leonid; Dubrovinskaia, Natalia (December 2019). "Synthesis of magnesium-nitrogen salts of polynitrogen anions". Nature Communications. 10 (1): 4515. doi:10.1038/s41467-019-12530-w. ISSN 2041-1723. PMC 6778147. PMID 31586062.
  5. R. H. Wentorf, Jr. (March 1961). "Synthesis of the Cubic Form of Boron Nitride". Journal of Chemical Physics. 34 (3): 809–812. doi:10.1063/1.1731679.
  6. Robert H. Wentorf, Jr. (October 1993). "Discovering a Material That's Harder Than Diamond". R&D Innovator. Retrieved June 28, 2006.

Further reading

  • Wu, P.; Tiedje, T. (2018). "Molecular beam epitaxy growth and optical properties of Mg3N2 films". Applied Physics Letters. AIP. 113 (8): 082101. doi:10.1063/1.5035560.
Salts and covalent derivatives of the nitride ion
NH3
N2H4
He(N2)11
Li3N Be3N2 BN β-C3N4
g-C3N4
CxNy
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 Ra3N2   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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