Sciencemadness Discussion Board

Salts of methazonic acid

Lotilko - 31-5-2017 at 08:54

It is known that aquaous solutions of sodium hydroxide react with nitromethane to form sodium nitronate, and then sodium methazonate. There's a synthesis about the acid at prepchem: http://www.prepchem.com/synthesis-methazonic-acid/

It mentions that the potassium salt is highly sensitive, while the ammonium salt readily decomposes forming hydrogen cyanide.

There is a video about the lead salt on youtube: https://youtube.com/watch?v=I0xX70b8Xwk
It's a rather weak primary, only denting a beer can. The comment section contains info about the silver, iron copper and zinc salts. The silver salt is said to be better, while the copper, iron and zinc exist as hydrates.

I would be interested about it's mercury and cadmium salts. Some cadmium salts are known to be better primers than their lead and mercury counterparts, especially azide, fulminate and some tetrazole derivatives. I was thinking that the salts could be prepared via a methatesis reaction between a water soluble acetate and sodium methazonate in a aquaous solution(or the free acid?) so the heavy metal salt precipitates out.

Any thoughts on this?

[Edited on 2017.5.31 by Lotilko]

PHILOU Zrealone - 2-6-2017 at 02:29

Yes nice primaries...I have made some Na methazonate the usual way and Ca methazonate from CaC2, water and nitromethane...but probably unpure.

I want to point out some critical information:
1°) Prepchem is lying about the preparation since from 45 gr nitromethane it is impossible to get 46 gr of methazonic acid...
2 CH3-NO2 --> HO-N=CH-CH2-NO2 <==> O=N-CH2-CH2-NO2
Onto the left side you have C2H6N2O4
Onto the right side you have C2H4N2O3...this means you have lost H2O into the dimerization process.
122 gr Nitromethane will at best deliver 104 gr Methazonic acid what means 15% mass loss
45 gr should give at best 38.25 gr

2°) The video of YouTube is cool but I suspect the product is unpure...I'm not sure the operator did the all Anders Hoveland's (Blastprep) process from nitromethane/NaOH...then acidification isolation of methazonic...reaction with NH4OH to get Ammonium methazonate and isolate it prior to reaction with the heavy metal soluble salt and recollect the precipitate.
To my feeling he simply by passed all this by reacting the soluble salt of heavy metal with the NM/NaOH result...where usually the NaOH is in excès to ensure the nitronic form to be present mainly.
As a consequence, you have a lot of white Pb(OH)2 together with the Pb(C2H3N2O3)2...this may explain that the lead salt is quite clear and only of tanned skin color...one would expect a deeper yellow, orange, red or brown color.

This means that if someone takes the care to do the full process to get a purer lead salt...it will be even more powerful...

[Edited on 2-6-2017 by PHILOU Zrealone]

Chisholm - 2-6-2017 at 07:23

Quote: Originally posted by PHILOU Zrealone  
I'm not sure the operator did the all Anders Hoveland's (Blastprep) process from nitromethane/NaOH


Whatever happened to that guy?

Lotilko - 4-6-2017 at 09:29

"The following improved method for the preparation of methazonic acid has been worked out: To a solution of NaOH (20g) in H2O (40 cc), at 45-50degC, nitromethane (20g) is added gradually, during 15 minutes. Towards the end of the addition the temperature is allowed to rise to 53degC. After remaining until it has cooled to 20degC, the liquid is neutralized with HCl (45cc, density 1.170) the temperature being kept below 10degC. This precipitates the methazonic acid. Yield, 13-15 g."

So is this the procedure you mentioned? If so, methazonic acid reacted with ammonia solution, isolation and methstesis with soluble heavy metal salt should yield the purest product?

Also, there are mentions about a basic salt of mercuric methazonate which is insoluble, but upon treatment with hydrochloric acid yields a crystalline water souble mercuric methazonate. If so, I believe the latter salt would have superior properties. How would one separate the mercuric methazonate from solution? Maybe evaporating the water and heating the resulting solids in vacuum, so ammonium chloride can sublime, leaving behind the mercuric salt?

Sorry if any errors are present in the above text, had a long day.

Cheers!

[Edited on 2017.6.4 by Lotilko]

PHILOU Zrealone - 5-6-2017 at 08:14

Quote: Originally posted by Lotilko  
"The following improved method for the preparation of methazonic acid has been worked out: To a solution of NaOH (20g) in H2O (40 cc), at 45-50degC, nitromethane (20g) is added gradually, during 15 minutes. Towards the end of the addition the temperature is allowed to rise to 53degC. After remaining until it has cooled to 20degC, the liquid is neutralized with HCl (45cc, density 1.170) the temperature being kept below 10degC. This precipitates the methazonic acid. Yield, 13-15 g."

So is this the procedure you mentioned? If so, methazonic acid reacted with ammonia solution, isolation and methstesis with soluble heavy metal salt should yield the purest product?

Also, there are mentions about a basic salt of mercuric methazonate which is insoluble, but upon treatment with hydrochloric acid yields a crystalline water souble mercuric methazonate. If so, I believe the latter salt would have superior properties. How would one separate the mercuric methazonate from solution? Maybe evaporating the water and heating the resulting solids in vacuum, so ammonium chloride can sublime, leaving behind the mercuric salt?

Sorry if any errors are present in the above text, had a long day.

Cheers!

[Edited on 2017.6.4 by Lotilko]

If you use an exes of NH3 (NH4OH) then you have OH(-) that will precipitate any heavy metal as hydroxyde and thus lowering the yield of pure methazonate salt.
The best option is to add a little excès of NH4OH to the methazonic acid to get 100% yield of NH4 methazonate and then to evaporate in dry air flow into the cold to get rid of the excès NH3 and water...

You are thus left with pure NH4 methazonate and traces of methazonic acid (due to some hydrolysis back during
evaporation but it must be minor due to slight excès of NH3).

Redissolve into demi water and do the methatesis. High concentration of NH4 methazonate and hevay metal soluble salt will help getting the normal salt...too diluted will bring more basic salts...

Hg methylnitronate turns into Hg fulminate upon standing...maybe Hg methazonate does the same or something related.

It is not smart to event think to heat a heavy (Hg) potentially sensitive to shock/heat/friction primary stuff in a way to sublimate NH4Cl...also won't the Hg chloride be unsoluble and stick as hell to the NH3 (Hg complexates easily with NH3).
Hg vapour may sublimate aswel...

Dry cold air (max 40°C) is the best way to dry the stuf to my feeling and it is wise to start low with the quantities and not to go too high of a quantity of dry material at one time in one single place just in case of a bad event.

Lotilko - 5-6-2017 at 13:31

After a bit of research it seems to me that the underlying chemistry is much more complex. Methazonic acid seems to form mono, and di salts, dependeing on reaction conditions. Experiments will tell.

What do you know about the ammonium salt? Does it have energetic properties, or just decomposes? You also mentioned a you have made the calcium salt. How does it perform? Is it hydrated?

[Edited on 2017.6.5 by Lotilko]

PHILOU Zrealone - 6-6-2017 at 01:45

Quote: Originally posted by Lotilko  
After a bit of research it seems to me that the underlying chemistry is much more complex. Methazonic acid seems to form mono, and di salts, dependeing on reaction conditions. Experiments will tell.

What do you know about the ammonium salt? Does it have energetic properties, or just decomposes? You also mentioned a you have made the calcium salt. How does it perform? Is it hydrated?

[Edited on 2017.6.5 by Lotilko]

Of course it is complex....
Some of the heavy metals are bivalent and may form mono salts (basic) or disalts...
In the following I use Pb/Lead as an example bivalent heavy metal...
Pb(2+) + 2 A(-) --> Pb(A)2
Pb(A)2 + H2O --> Pb(OH)(A) + HA

And methazonic is a diacid...
There is the oximic part HO-N=C
and
the nitronic part C=N(O)-OH
This of course add to the complexity of the reaction because you may have:
HO-N=CH-CH=NO2-Pb-O2N=CH-CH=NOH thus Pb(C2H3N2O3)2

(-Pb-O-N=CH-CH=NO2-)n thus Pb(C2H2N2O3)1

and the basic salt
HO-Pb-O2N=CH-CH=NOH thus Pb(C2H4N2O4)1

Of course the first one is the most suited/wished because it contains more explosive organic stuf and thus less dead weight metal for a better energy output...

About the NH4 salt...I know not much...it is dark brown orange into solution, deliquescent/hygroscopic and when dry not very energetic. It turns resinous upon storage and release constantly a smell of NH3 (constant hydrolysis back to NM and NH3)

The Ca salt is a solid precipitate but probably unpure owing to formation of Ca(OH)2 from CaC2 and water...also CaC2 is itself not a pure compound...
When dry, the powder do crackelings and tiny explosions when exposed to a flame...nowhere near as fun as detonating compounds like SADS/SANC or NiHN.

Maybe that doing the experiment again with chemically pure Ca(OH)2 nearly saturated solution (lime water) would be good to get a purer compound...and validate it as potential energetic material or disqualify it...

[Edited on 6-6-2017 by PHILOU Zrealone]

Velzee - 6-6-2017 at 06:51

Excuse my ignorance, but where can nitromethane be purchased/obtained?

PHILOU Zrealone - 6-6-2017 at 11:06

Quote: Originally posted by Velzee  
Excuse my ignorance, but where can nitromethane be purchased/obtained?

Did you really searched before asking?
There are countless treads/posts here about this...and a simple Google search would tell you a lot...

-From chemical companies
-From special racing fuel providers
-If you have a good lab you could do your own
Via diluted HNO3/Methane (arround 450°C) or HNO3/Ethane (arround 400°C).
Via chloracetic acid and NaNO2
Via CH3X (X = Br or I) and dry AgNO2
Via isomerization of CH3ONO (probably dangerous)
...

Chisholm - 6-6-2017 at 18:58

Nitromethane is one of the few things that can readily dissolve Krazy Glue and Super Glue, so products that remove those can be good sources of nitromethane.

If you can't find straight nitromethane where you live, companies provide RC fuel comprising NM/methanol blends that are up to 30% nitromethane by mass. The methanol can be separated via distillation, though it takes about 8% of the nitromethane with it due to the formation of an azeotrope.

PHILOU Zrealone - 7-6-2017 at 02:52

Quote: Originally posted by Chisholm  
Nitromethane is one of the few things that can readily dissolve Krazy Glue and Super Glue, so products that remove those can be good sources of nitromethane.

If you can't find straight nitromethane where you live, companies provide RC fuel comprising NM/methanol blends that are up to 30% nitromethane by mass. The methanol can be separated via distillation, though it takes about 8% of the nitromethane with it due to the formation of an azeotrope.

If the aim is to make nitroisobutylglycerol ...no need to separate first the two...simply put the formaldehyde and base into the mix and only after do care for the separation...

Chisholm - 7-6-2017 at 06:21

Is nitroisobutylglycerol more soluble in water or in methanol?

EDIT: wrong thread?

[Edited on 6-7-2017 by Chisholm]

Lotilko - 7-6-2017 at 11:49

It hit me that one could try chlorinating the methazonic acid, in an alcoholic solution, excluding any water, so the intermediate does not hydrolise, followed by a Ter-Meer reaction to form the dinitroacetaldoxime. It may be worth a try.

Even pure Ca-methazonate might be hydrated, which lends inferior properties. If I rember correctly, Ca, Mg and Ba salts form hydrates with many acids which are very hard to dehydrate. Ca and Ba picrates detonate before losing crystal water, so I think transition metals like Ti, Cd and Tl might be better initators.

PHILOU Zrealone - 7-6-2017 at 13:53

Quote: Originally posted by Chisholm  
Is nitroisobutylglycerol more soluble in water or in methanol?

EDIT: wrong thread?

[Edited on 6-7-2017 by Chisholm]

Should be quite soluble in both because all polar and all holding hydrophilic groups OH...