Magnesium nitride

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Magnesium nitride
Magnesium nitride.jpg
Mg3P2.png
Names
IUPAC name
Magnesium nitride
Other names
trimagnesium dinitride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.031.826 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 235-022-1
PubChem CID
UNII
  • InChI=1S/3Mg.2N
  • InChI=1S/3Mg.2N/q3*+2;2*-3
  • InChI=1S/3Mg.2N/q;;+2;2*-1
  • [Mg+2].[Mg+2].[Mg+2].[N-3].[N-3]
Properties
Mg3N2
Molar mass 100.9494 g/mol
Appearancegreenish yellow powder
Density 2.712 g/cm3
Melting point approx. 1500°C
Hazards [1]
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-exclam.svg
Danger
H228, H315, H319, H335
P210, P261, P280, P305+P351+P338, P405, P501
Safety data sheet (SDS) External MSDS
Related compounds
Other cations
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Magnesium nitride, which possesses the chemical formula Mg 3 N 2, is an inorganic compound of magnesium and nitrogen. At room temperature and pressure it is a greenish yellow powder.

Contents

History

When measuring the boiling point of magnesium, Henri Étienne Sainte-Claire Deville and Henri Caron identified that molten magnesium they distilled covered itself by "small colorless and transparent needles which are destroyed fairly quickly by transforming into ammonia and magnesia". In their 1857 publication the chemists interpreted it as a likely nitride similar to those discovered by Friedrich Wöhler and Heinrich Rose. [2]

It was indeed confirmed in 1862 when Friedrich Briegleb and Johann Georg Anton Geuther synthesized the compound on purpose and first studied it. [3]

Preparation

3 Mg + N2 → Mg3N2
3 Mg + 2 NH3 → Mg3N2 + 3 H2

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. [4] [5] [6] These include the Mg2N4 and MgN4 solids which both become thermodynamically stable near 50 GPa. [7] The Mg2N4 is composed of exotic cis-tetranitrogen N4−4 species with N-N bond orders close to one. This Mg2N4 compound was recovered to ambient conditions, along with the N4−4 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). [8]

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 [9] ), 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 [10] It has also been proposed as an intermediate in a fossil-fuel-free nitrogen fixation process. [11]

Related Research Articles

<span class="mw-page-title-main">Boron nitride</span> Refractory compound of boron and nitrogen with formula BN

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form.

<span class="mw-page-title-main">Haber process</span> Industrial process for ammonia production

The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. It converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using finely divided iron metal as a catalyst:

<span class="mw-page-title-main">Nitrogen</span> Chemical element with atomic number 7 (N)

Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colourless and odourless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant chemical species in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.

<span class="mw-page-title-main">Aluminium nitride</span> Nitride of aluminum

Aluminium nitride (AlN) is a solid nitride of aluminium. It has a high thermal conductivity of up to 321 W/(m·K) and is an electrical insulator. Its wurtzite phase (w-AlN) has a band gap of ~6 eV at room temperature and has a potential application in optoelectronics operating at deep ultraviolet frequencies.

<span class="mw-page-title-main">Superhard material</span> Material with Vickers hardness exceeding 40 gigapascals

A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are virtually incompressible solids with high electron density and high bond covalency. As a result of their unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools, disc brakes, and wear-resistant and protective coatings.

In chemistry, a nitride is a chemical compound of nitrogen. Nitrides can be inorganic or organic, ionic or covalent. The nitride anion, N3- ion, is very elusive but compounds of nitride are numerous, although rarely naturally occurring. Some nitrides have a found applications, such as wear-resistant coatings (e.g., titanium nitride, TiN), hard ceramic materials (e.g., silicon nitride, Si3N4), and semiconductors (e.g., gallium nitride, GaN). The development of GaN-based light emitting diodes was recognized by the 2014 Nobel Prize in Physics. Metal nitrido complexes are also common.

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

Lithium nitride is an inorganic compound with the chemical formula Li3N. It is the only stable alkali metal nitride. It is a reddish-pink solid with a high melting point.

<span class="mw-page-title-main">Borazine</span> Boron compound

Borazine, also known as borazole, is an inorganic compound with the chemical formula B3H6N3. In this cyclic compound, the three BH units and three NH units alternate. The compound is isoelectronic and isostructural with benzene. For this reason borazine is sometimes referred to as “inorganic benzene”. Like benzene, borazine is a colourless liquid with an aromatic odor.

<span class="mw-page-title-main">Robert H. Wentorf Jr.</span>

Robert H. Wentorf Jr. was a staff scientist at General Electric Corporate Research and Development Laboratory in Schenectady, N.Y. and a professor of chemical engineering at Rensselaer Polytechnic Institute in Troy, N.Y.

<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:

<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">Boron compounds</span>

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

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.

In chemistry, ammonolysis (/am·mo·nol·y·sis/) is the process of splitting ammonia into . Ammonolysis reactions can be conducted with organic compounds to produce amines (molecules containing a nitrogen atom with a lone pair, :N), or with inorganic compounds to produce nitrides. This reaction is analogous to hydrolysis in which water molecules are split. Similar to water, liquid ammonia also undergoes auto-ionization, , where the rate constant is k = 1.9 × 10-38.

The inorganic imide is an inorganic chemical compound containing

<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.

Polynitrides are solid chemical compounds with a large amount of nitrogen, beyond what would be expected from valencies. Some with N2 ions are termed pernitrides. Azides are not considered polynitrides, although pentazolates are.

Molybdenum nitride (Mo2N) is a binary inorganic compound composed of molybdenum and nitrogen. It belongs to the family of transition metal nitrides and exhibits properties that make it useful in applications such as a catalyst and a coating material.

Manganese nitrides are salts of manganese and the nitride ion. Four of these compounds are stable at atmospheric pressure. The most important is Mn3N2, which catalyzes nitrogen fixation and is a high-temperature antiferromagnet. The others are Mn6N5–6, Mn4N, and Mn2N. The compounds generally form as surface layer during combustion of manganese metal in nitrogen or ammonia gas, and homogenous samples can be difficult to obtain.

References

  1. "Summary of Classification and Labelling" . Retrieved 4 December 2021.
  2. s:fr:Page:Comptes rendus hebdomadaires des séances de l’Académie des sciences, tome 044, 1857.djvu/406
  3. Briegleb, Fr.; Geuther, A. (1862). "Ueber das Stickstoffmagnesium und die Affinitäten des Stickgases zu Metallen". Justus Liebigs Annalen der Chemie (in German). 123 (2): 228–241. doi:10.1002/jlac.18621230212. ISSN   1099-0690.
  4. 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.
  5. 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. Bibcode:2017PCCP...19.9246W. doi:10.1039/C6CP08771J. ISSN   1463-9076. PMID   28322368.
  6. 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. S2CID   132258000.
  7. 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. Bibcode:2019NatCo..10.4515L. doi:10.1038/s41467-019-12530-w. ISSN   2041-1723. PMC   6778147 . PMID   31586062.
  8. R. H. Wentorf, Jr. (March 1961). "Synthesis of the Cubic Form of Boron Nitride". Journal of Chemical Physics. 34 (3): 809–812. Bibcode:1961JChPh..34..809W. doi:10.1063/1.1731679.
  9. Robert H. Wentorf, Jr. (October 1993). "Discovering a Material That's Harder Than Diamond". R&D Innovator. Retrieved June 28, 2006.
  10. Zong, Fujian; Meng, Chunzhan; Guo, Zhiming; Ji, Feng; Xiao, Hongdi; Zhang, Xijian; Ma, Jin; Ma, Honglei (2010). "Synthesis and characterization of magnesium nitride powder formed by Mg direct reaction with N2". _Journal of Alloys and Compounds. 508 (1): 172–176. doi:10.1016/j.jallcom.2010.07.224.
  11. Hu, Yang; Chen, George Z.; Zhuang, Lin; Wang, Zhivong; Jin, Xianbo (2021). "Indirect electrosynthesis of ammonia from nitrogen and water by a magnesium chloride cycle at atmospheric pressure". Cell Reports Physical Science. 2 (5): 100425. Bibcode:2021CRPS....200425H. doi: 10.1016/j.xcrp.2021.100425 . ISSN   2666-3864. S2CID   235555007.

Further reading