Magnesium nitride explained

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

Preparation

• By passing dry nitrogen over heated magnesium at 800 °C:

• or ammonia at 700 °C:

Chemistry

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

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 and solids which both become thermodynamically stable near 50 GPa.^[4] The is composed of exotic cis-tetranitrogen species with N-N bond orders close to one. This compound was recovered to ambient conditions, along with the units, marking only the fourth polynitrogen entity bulk stabilized at ambient conditions.

Uses and history

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

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.

Magnesium nitride has also been applied to synthesize aluminum nitride nanocrystals, cubic boron nitride and nitrides of aluminum and Group 3 ^[7] It has also been proposed as an intermediate in a fossil-fuel-free nitrogen fixation process.^[8]

Further reading

• Wu, P. . Tiedje, T. . 2018. Molecular beam epitaxy growth and optical properties of Mg₃N₂ films . Applied Physics Letters . 113 . 8 . 082101 . . 10.1063/1.5035560 . 2018ApPhL.113h2101W . 125356057.

Notes and 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. 10.1021/acs.jpcc.7b00474. 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. 10.1039/C6CP08771J. 28322368. 2017PCCP...19.9246W. 1463-9076.
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. 10.1021/acs.jpcc.8b12527. 132258000. 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. 10.1038/s41467-019-12530-w. 2041-1723. 6778147. 31586062. 2019NatCo..10.4515L.
5. R. H. Wentorf, Jr.. Robert H. Wentorf, Jr.. March 1961. Synthesis of the Cubic Form of Boron Nitride. Journal of Chemical Physics. 34. 3. 809–812. 10.1063/1.1731679 . 1961JChPh..34..809W.
6. Web site: Discovering a Material That's Harder Than Diamond. June 28, 2006. Robert H. Wentorf, Jr.. October 1993. R&D Innovator.
7. Zong. Fujian. Meng. Chunzhan. Guo. Zhiming. Ji. Feng. Xiao. Hongdi. Zhang. Xijian. Ma. Jin. Ma. Honglei. Synthesis and characterization of magnesium nitride powder formed by Mg direct reaction with N2. _Journal of Alloys and Compounds. 2010 . 508. 1. 172–176. 10.1016/j.jallcom.2010.07.224.
8. Hu. Yang. Chen. George Z.. Zhuang. Lin. Wang. Zhivong. Jin. Xianbo. Indirect electrosynthesis of ammonia from nitrogen and water by a magnesium chloride cycle at atmospheric pressure. Cell Reports Physical Science. 2021 . 2. 5. 100425. 2666-3864. 10.1016/j.xcrp.2021.100425. 2021CRPS....200425H . 235555007 . free.