Sciencemadness Discussion Board

Nitration mix from bisulfate and nitrate?

PoWEr - 15-5-2025 at 02:24

I have been looking for alternatives to sulfuric and nitric acid (specifically nitric acid) to make a nitration mix for nitrobenzene, wouldn't using a simple nitrate and bisulfate salt be enough?

Maui3 - 15-5-2025 at 03:55

They are both solids, so I suppose you would need a solvent that cannot be nitrated and they are both soluble in. But from experience sodium bisulfate doesn't work well (at least for me). I assume you are asking because you can't get conc. sulfuric acid legally in Poland :P. You can use methanesulfonic acid instead?

Maui3 - 15-5-2025 at 03:59

But I think sodium bisulfate + nitrate salt will just generate nitric acid, not the nitronium ion.
I read somewhere that you can use acetic anhydride + nitric acid. But then you'd still have to get the nitric acid.
You can use nitrate salt + sulfuric acid instead of nitric acid + sulfuric acid, I am pretty sure.

jackchem2001 - 15-5-2025 at 04:13

Sulfuric + nitrate salt works for alcohols, not sure about aromatics. Bisulfate + nitrate salt seems pretty unlikely to work given the pKas of acids (bisulfate and nitric). The energetics people would have good answers

Sulaiman - 15-5-2025 at 04:43

Quite a lot of relevant info. and references in the Wikipedia article 'Nitration'
https://en.m.wikipedia.org/wiki/Nitration
Phosphoric acid is mentioned.
(and phosphoric acid + nitrate = nitric acid + insoluble phosphate)
(decant or filter, distil for near az. nitric acid)
(I don't know if a one pot phosphoric + nitrate would work)
not my area but I think that many nitrations rely upon the dehydrating properties of exces az. sulphuric to mop up water molecules.

PoWEr - 15-5-2025 at 08:43

Quote: Originally posted by Sulaiman  
Quite a lot of relevant info. and references in the Wikipedia article 'Nitration'
https://en.m.wikipedia.org/wiki/Nitration
Phosphoric acid is mentioned.
(and phosphoric acid + nitrate = nitric acid + insoluble phosphate)
(decant or filter, distil for near az. nitric acid)
(I don't know if a one pot phosphoric + nitrate would work)
not my area but I think that many nitrations rely upon the dehydrating properties of exces az. sulphuric to mop up water molecules.


It seems like phosphoric acid is an option, I have found a video on using a nitration mix from phosphoric and nitric acid:
https://www.youtube.com/watch?v=0zcqeaJfY-8

And another one that experimented with cotton instead:
http://www.sciencemadness.org/talk/viewthread.php?tid=138707

Also using a high (>95%) nitric acid concentration makes the requirement of another acid optional, though as someone else pointed out in that thread, it may just explode and is just too dangeous:
https://www.sciencemadness.org/whisper/viewthread.php?tid=52...

Well, then there's still the problem of nitric acid alternative, no idea if a nitrate salt would work.

Alkoholvergiftung - 15-5-2025 at 09:55

Sulfuric acid, Phosphoric acid , Glacial acetic acid, and there anhydrides can be used with nitric acid for nitration. Source. Technologie der Sprengstoffe from Rudolf Biedermann. Phosphoric acid made more stable Gun cutton because it dosnt attack the nitro cellulose. Source Urbanski.

Displacment dosnt neccecary need an stronger acid but an less volatile one.
F. Kuhlmann. Nitric acid can be made (and was made) from Epson Salt and Saltpeter in Spain. MnCl2 and Chile Saltpeter in France around 230C for this reaction.
In heat nitric acid can displaced "destilled with phosphoric acid, Boric acid, and the very weak silicic acid".
Older book wrote the same for sulfuric acid can be made with phosporic acid and boric acid if the destillation temperature is above the boiling point of the Concentrated acid.

[Edited on 15-5-2025 by Alkoholvergiftung]

[Edited on 15-5-2025 by Alkoholvergiftung]

[Edited on 16-5-2025 by Alkoholvergiftung]