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Do all group 13 elements react with nitrogen to form nitrides of form $\ce{MN}?$

J.D. Lee's Inorganic chemistry book mentions the following:

Aluminium burns in dinitrogen at high temperatures forming $\ce{AlN}.$ The other elements do not react.

However, a reaction of boron with nitrogen is mentioned elsewhere:

$$\ce{2B + N2 -> 2BN}$$

I'm assuming these boron and aluminium do react. Do gallium, indium and thallium react with nitrogen as well?

Please post your answer mentioning a reliable reference or source.

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    $\begingroup$ Boron nitrides are a real thing. Gallium and indium are as well (and wide band gap semiconductors). not sure if they are focusing on the 'react' part. Not sure about thallium... $\endgroup$
    – Jon Custer
    Mar 31, 2021 at 13:25
  • $\begingroup$ Yeah I've seen gallium and indium nitrides been referred to at some places too, but my question is whether they can be formed by direct reaction with dinitrogen. $\endgroup$
    – Ashish
    Mar 31, 2021 at 13:26
  • $\begingroup$ Well, it turns out N2 is really hard to break up for a reaction. For example, you can't react iron with N2 - you need to use ammonia (or a plasma source to get atomic N). You will note that air is 80% N2, and many metals are perfectly happy with N2 (not so much O2). In general, both gallium and indium are perfectly happy sitting around in air. $\endgroup$
    – Jon Custer
    Mar 31, 2021 at 13:29
  • $\begingroup$ @JonCuster sciencedirect.com/science/article/abs/pii/S0254058419300914 $\endgroup$ Mar 31, 2021 at 13:40
  • $\begingroup$ Cool. I would not consider reactive sputtering to be reacting with N2 - the plasma provides atomic nitrogen. $\endgroup$
    – Jon Custer
    Mar 31, 2021 at 13:43

2 Answers 2

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All group 13 elements (can technically) form nitrides from the direct combination of the elements (elemental reaction).

  1. Boron: See @Oscar's answer. Also, see references(1,2)
  2. Aluminum: There is a paper(3) which discussed about combustion of aluminum in a high-temperature and high pressure (up to 300 MPa) nitrogen atmosphere to form aluminum nitride.
  3. Gallium: Gallium nitride is formed by the direct combination of elements at 1200 °C.
  4. Indium: Direct combination of indium and nitrogen cannot be done due to factors like dissociation of $\ce{InN}$ at around 550 °C and high-equilibrium partial pressure of nitrogen over $\ce{InN}$ films. So, a technique called ion-implantation is used to obtain indium nitride nanoclusters over silica matrix. There is also a certain low-temp reaction (250°C) of indium iodide and nitrogen to obtain indium nitride.
  5. Thallium: Thallium nitride has been synthesized in a film form by DC reactive sputtering of metal thallium in nitrogen.

References

  1. https://www.osti.gov/servlets/purl/591090
  2. Direct elementary reactions of boron and nitrogen at high pressures and temperatures C. S. Yoo, J. Akella, H. Cynn, and M. Nicol, Phys. Rev. B 56, 140 (1997), DOI: https://doi.org/10.1103/PhysRevB.56.140
  3. Loryan, V.É., Borovinskaya, I.P. Aluminum Combustion in Nitrogen. Combustion, Explosion, and Shock Waves 39, 525–533 (2003). https://doi.org/10.1023/A:1026105600954
  4. Nitrogen Compounds of Gallium. III, W. C. Johnson, J. B. Parson, and M. C. Crew The Journal of Physical Chemistry 1932 36 (10), 2651-2654 DOI: 10.1021/j150340a015
  5. P. Santhana Raman, K.G.M. Nair, Jay Ghatak, Umananda M. Bhatta, P.V. Satyam, S. Kalavathi, B.K. Panigrahi & V. Ravichandran (2013) Formation of embedded indium nitride and indium oxide nanoclusters in silica samples sequentially implanted with indium and nitrogen ions, Journal of Experimental Nanoscience, 8:7-8, 957-964, DOI: 10.1080/17458080.2011.630034
  6. Indium nitride from indium iodide at low temperatures: synthesis and their optical properties by Changzheng Wu et.al., New J. Chem., 2005,29, 1610-1615, https://doi.org/10.1039/B510426B
  7. Synthesis and properties of thallium nitride films, L.R.Shaginyan, Materials Chemistry and Physics, Volume 227, 2019 , Pages 157-162, https://doi.org/10.1016/j.matchemphys.2019.02.005
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  • $\begingroup$ Good summary here +1. Given the relatively low stability of Tl(III) and nitrogen being only a modest reducing agent, the formation of thallium nitride as a 1:1 compound is fairly interesting. $\endgroup$ Apr 7, 2021 at 13:41
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In the case of boron, a reaction with nitrogen does occur under some eye-popping conditions:

Combustion of boron powder in nitrogen plasma at 5500 °C yields ultrafine boron nitride used for lubricants and toners.[1]

The characteristic molecular thermal energy $kT$ at this temperature is roughly half an electron volt, which is enough to at least partially break a significant fraction of the nitrogen-nitrogen bonds. The boron is also vaporized at this temperature, and both of these factors facilitate the reaction. Vaporizing the boron also favors forming the fine particles which are desired for the lubricant and toner applications noted above.

Most boron nitride, not requiring the ultrafine particles, is synthesized by metathesis reactions under more typical industrial conditions, which are also given in the WP article noted above. These commonly involve boron oxide, which both becomes fluid at much lower temperatures than the element and can act as an acid towards basic nitrogen sources such as ammonia.

Cited Reference

1. Paine, Robert T.; Narula, Chaitanya K. (1990). "Synthetic Routes to Boron Nitride". Chemical Reviews90: 73–91.

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