Sciencemadness Discussion Board

5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends

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MineMan - 19-12-2018 at 21:52

Why so much love for DBX-1? It’s VOD is high, it’s lead free but is it not still pretty sensitive?

snooby - 20-12-2018 at 03:25

https://www.researchgate.net/publication/288871303_Recent_Ad...

This article include some detailed info about impurities in raw nantz.

wessonsmith - 29-6-2019 at 10:03

Quote: Originally posted by MineMan  
Why so much love for DBX-1? It’s VOD is high, it’s lead free but is it not still pretty sensitive?


Yeah, I agree. I have made some of the nitrotetrazole salts, silver(AgNTz), copper(DBX-1), and Sodium(NaNTz). I have even made the Nickel salt from NaNTz. The Nickel looks very similar to NHN in color but will not separate out into a fine powder when suction filtered.

They are all very sensitive with NaNTz being the exception. NaNTz can't be used by itself in the Dihydtare form, it's too difficult to set off.

The nitrotetrazole salts are more stable and less reactive then Lead Azide but just as sensitive. So for those companies who use LA, DBX-1 is a direct replacement, and no machinery changes are necessary. For the rest of us, they still don't offer any advantage over primaries like NHN and are more expensive to manufacture.

wessonsmith - 29-6-2019 at 10:11

Quote: Originally posted by snooby  
https://www.researchgate.net/publication/288871303_Recent_Ad...

This article includes some detailed info about impurities in raw NaNTz.


This doesn't apply to those who are manufacturing NaNTz using the 2017 Batch Method patent.

Microtek - 29-6-2019 at 10:55

I have experimented with the complexes in the "Green primaries" paper (transition metal complexes with nitrotetrazole amine and water). They are about equivalent with NHN in sensitivity and power, but makes DDT more reliably.

Mychemlife - 21-7-2019 at 09:09

Has anyone ever crystalized out any Na,(NTZ)

Screenshot_20190720-213531.png - 1.1MB

snooby - 4-11-2019 at 09:47

Since there are sooo many synths about nant, what is your favoriete? The facile methode give me a very yellow end product. Still kt works, but not like this: https://youtu.be/U-1bNouTHhQ

My solution Just turns green.
Edit: i usde this one: https://patents.google.com/patent/US9598380B2/en

I notice a lot of red Times, no maybe to fast addition rate waht explanins the color.

[Edited on 4-11-2019 by snooby]

fusso - 4-11-2019 at 10:47

Great crystals!!!

snooby - 4-11-2019 at 11:00

Whats your method of maling the nantz and het the clear crystals?

B.D.E - 14-3-2020 at 13:39

nevermind, please delete.
apologies.

[Edited on 14-3-2020 by B.D.E]

Etanol - 13-4-2020 at 13:04

How to prepare the NH4-nitrotetrazole from Na-nitrotertazole?
Na-NTz+H2SO4=>NTz ?
NTz+NH3 (water)=>NH4NTz ?
Is exist the short way?
I wish green primaryes)

NeonPulse - 21-4-2020 at 08:00

Quote: Originally posted by Mychemlife  
Has anyone ever crystalized out any Na,(NTZ)


Sure have. But via recrystallising crude product in minimal Water first and second from Acetone. The greenish tint was replaced by Snow White colour.
These crystals you have look very nice and quite well formed. Nice job.

B(a)P - 18-5-2020 at 16:21

Yesterday I conducted a synthesis of 5-ATZ. I have done this reaction 3 other times, always following the Engager method, starting with aminoguanidine bicarbonate, presented earlier in this thread. The only way I deviate from Engagers write up is to add sodium carbonate until my solution is at pH 5.5 rather than adding the exact mass presented in the paper. Each time my yield of 5-ATZ has been around 70 to 80% based on aminoguanidine bicarbonate.
This time the changes in colour that I noted on my previous attempts did not quite match up. I also needed less sodium carbonate than I had previously used. I didn't question this as much as I should have.
At the completion of reflux I adjusted the pH to 3 and left the solution to cool.
After cooling no product was visible, which is normal given 5-ATZ readily produces supersaturated solutions. I tried agitating, but this did not work. I drew off 3 mls and warmed it on an evaporating dish to produce a seed crystal then inserted that into the main solution. After about 8 hours a small mass of needle like crystals precipitated. At this point I stopped and reviewed what I had done. I reviewed my notes and other than the differences mentioned above I couldn't see where I had gone wrong. I tried checking my pH and my meter was toast. I checked it with indicator paper and found it to be at around 1! It seems my pH meter was on its last legs during the synthesis and so I likely refluxed at a less than optimal pH. The crystallisation would also have occurred at a pH that was sub-optimal, though I understand this is not so critical as the pH for the reflux.
My question is what have I ended up with? I have done some research and can't find much on side products that might dominate at lower temperates. Yield is very low. My crystalline product is transparent, colourless and needle like to 10 mm in length. For scale the stir bar is 25 mm in length. The melting point of the product seems about right for 5-ATZ and it decomposes at about the right temperature in a way I would expect it to. My thoughts are a very low yield and as a result the product has crystallised very slowly. Does anyone have any resources that go into depth on the side reactions that occur for this reaction? Thanks in advance for any assistance!

5ATZ_2.jpg - 2.6MB 5ATZ_1.jpg - 1.8MB

B(a)P - 19-9-2020 at 01:36

Cadmium nitrotetrazole
0.5 g of cadmium was dissolved in 1.5 g of 70 percent HNO3 and a little dH2O
The cadmium nitrate was added to a solution of 0.5 g of nitrotetrazole in 2 ml dH2O.
A white precipitate of cadmium nitrotetrazole (CdNTZ) formed immediately with a slight exotherm.
On drying the precipitate shrunk in size considerably.
The CdNTZ was readily soluble in water.
CdNTZ is slightly friction sensitive and moderately impact sensitive.
CdNTZ is sensitive to direct and indirect heating and donates before melting in amounts almost too small to see.

Question about NaNT purification

pdb - 6-5-2021 at 23:01

I refer to "Facile method for preparation of NaNT" (US9,598,380). It works well and is indeed very easy. But I am intrigued by the 1:2 molar ratio of 5-AT to NaNO2: this means that if one mole of Na gives NaNT, another mole of Na goes into the solution and pollutes it. But in what form? NaNO3, or an excess of NaNO2, or what else? We should know this before trying to find a method to purify NaNT. Does anyone know how to write the reaction between 5-AT, NaNO2 and HNO3?


[Edited on 7-5-21 by pdb]

Advice from someone who has successfully prepared crystalline DBX-1

pdb - 11-5-2021 at 05:30

I have prepared DBX-1 according to Fronabarger twice, with similar results. I have no doubt about the nature of the product, which deflagrates on contact with flame and detonates on heat or under light confinement. On the other hand, I observe that the product, when dried on a filter, appears as lumps, which leave a fine sticky dust on the finger when touched. Under the microscope, this powder appears amorphous. Moreover, its density is low, and even under high pressure it is difficult to reduce its volume: for the same weight, it is 4 to 5 times more voluminous when pressed than AgN3 for example. Also, I wonder if I missed the crystallisation step: according to Fronabarger, at about one third of the addition of the ascorbate, the product starts to precipitate and the solution takes on a rusty colour within a few minutes. I have observed these changes, but still my DBX-1 appears amorphous, and in this form I do not see how it could replace Pb(N3)2 according to the drop-in replacement principle.

Also, I would be interested in having someone who has obtained DBX-1 in crystalline form look at the attached photos to tell me if any differ from their own experience. Thank you!

(sorry, the pictures are in reverse order)
(the microscope pics are 1 mm in lenth)



DBX-1 1.jpg - 43kB DBX-1 2.jpg - 38kB 20210510_120622.jpg - 604kB 20210507_190039.jpg - 535kB 20210510_151550.jpg - 323kB 20210507_165210.jpg - 333kB 20210507_163520.jpg - 337kB 20210507_161754.jpg - 357kB 20210507_160910.jpg - 373kB 20210507_160643.jpg - 448kB

[Edited on 11-5-21 by pdb]

DBX Labs - 21-5-2021 at 14:39

From my experience making DBX-1, I'll get a near identical amorphous brown sludge most every time I run from scratch. The sludge dries into chunks just like yours that are flame sensitive and detonate when confined and heated. However, I have never been able to get this first product to detonate confined with a fuse, even as a powder.
What I've found and and have yet to publish in a video is that when I've taken a small amount (~2-3 grams) of this amorphous product and fed it into a repeated synthesis from scratch, the impure DBX-1 present in the first product catalyzes the formation of much more visible DBX-1 crystals that are red rather than brown. Additionally, it appears much less gelatinous sludge remains intermixed with the product in this case.
Hope this helps.

pdb - 22-5-2021 at 06:18

Quote: Originally posted by DBX Labs  
the impure DBX-1 present in the first product catalyzes the formation of much more visible DBX-1 crystals that are red rather than brown. Additionally, it appears much less gelatinous sludge remains intermixed with the product in this case.


This effect is reported by Ford (from line 46). I'll give it a try myself.



Attachment: 2015 DBX-1-Ford.pdf (929kB)
This file has been downloaded 733 times

FanofYellow - 11-2-2022 at 21:47

Hi guys, if you're following DBX labs (ReactiveChem) procedure with NaNO2+H2SO4, make sure to keep your temps within +5c of specified temperature (65 degrees) or you're gonna get some micro detonations and have a scary time.


First one scared the hell out of me. Thought my Chinaware was preparing to shatter, did a quick recon and just about the time I put the pieces together and realized what was happening the SECOND one happened. This occurred with the following setup:

Solution 1:
2g 5-ATZ
1.36mL H2SO4 (93%)
10mL Water

Solution 2 (to be added to solution 1):
5.68g NaNO2
20mL Distilled Water

Temperature was about 72 degrees when I did maybe the fifth 1.5mL addition of solution 2 into solution 1. Being done on a round bottom flash inside of my stirring heating mantle.

edit: was also blowing air into reaction flask to help clear evolved NO2. Maybe that contributed to the micro detonations


[Edited on 12-2-2022 by FanofYellow]

FanofYellow - 12-2-2022 at 14:29

What do you guys think? NaNTZ synthesis I panicked over yesterday. I don't know if that's the final product though, methinks I might have made sodium nitrate, those big crystals decompose into NOx on heating, but they do crackle

Screenshot_20220212-162223-423.png - 855kB

B(a)P - 12-2-2022 at 23:22

That kind of looks like 5 aminotetrazole. Nitrotetrazole should do not then crackle.

FanofYellow - 14-2-2022 at 12:00

Quote: Originally posted by FanofYellow  
What do you guys think? NaNTZ synthesis I panicked over yesterday. I don't know if that's the final product though, methinks I might have made sodium nitrate, those big crystals decompose into NOx on heating, but they do crackle


Quote: Originally posted by B(a)P  
That kind of looks like 5 aminotetrazole. Nitrotetrazole should do not then crackle.



My beautiful crystals nooooo.... Instead of crackling on heating my (formerly) beautiful crystals turned to completely nonflammable white powder. Testing my end product with Silver Nitrate solution precipitated out some insoluble white stuff which pretty much confirms I've made sodium sulfate... Oh well, back to the bench to try again.

B(a)P - 14-2-2022 at 13:58

Quote: Originally posted by FanofYellow  
Hi guys, if you're following DBX labs (ReactiveChem) procedure with NaNO2+H2SO4, make sure to keep your temps within +5c of specified temperature (65 degrees) or you're gonna get some micro detonations and have a scary time.


First one scared the hell out of me. Thought my Chinaware was preparing to shatter, did a quick recon and just about the time I put the pieces together and realized what was happening the SECOND one happened. This occurred with the following setup:

Solution 1:
2g 5-ATZ
1.36mL H2SO4 (93%)
10mL Water

Solution 2 (to be added to solution 1):
5.68g NaNO2
20mL Distilled Water

Temperature was about 72 degrees when I did maybe the fifth 1.5mL addition of solution 2 into solution 1. Being done on a round bottom flash inside of my stirring heating mantle.

edit: was also blowing air into reaction flask to help clear evolved NO2. Maybe that contributed to the micro detonations


[Edited on 12-2-2022 by FanofYellow]


I only just read this first post properly. You should not get detonations with this reaction, nor should it be so touchy within 5C of the recommended temperature. You should have added the ATZ solution to the nitrite, not the other way around, that is your problem.

magneet - 16-10-2022 at 11:34

Quote:
Question about NaNT purification


I refer to "Facile method for preparation of NaNT" (US9,598,380). It works well and is indeed very easy. But I am intrigued by the 1:2 molar ratio of 5-AT to NaNO2: this means that if one mole of Na gives NaNT, another mole of Na goes into the solution and pollutes it. But in what form? NaNO3, or an excess of NaNO2, or what else? We should know this before trying to find a method to purify NaNT. Does anyone know how to write the reaction between 5-AT, NaNO2 and HNO3?

[Edited on 7-5-21 by pdb]


According to this patent:
https://patents.google.com/patent/US9718791B2/en
Here the slight excess of nitrite is added to control PH somewhat during the reaction in the "continuous flow system" (not to be confused with the batch method).

From that same patent:
Quote:
In the embodiments where the nitrite reactant is added in excess for pH control, the excess nitrite is still present in the reactant mixture 26 after the substitution reaction has reached completion. To remove the excess nitrites, additional acid may be added to the reactant mixture 26 at any one or more of various suitable locations, which include but are not limited to a late stage of the reaction zone 28 at a point where the reaction is nearing or at completion; at the point where the reactant mixture 26 exits the processing zone 18; and/or after the reactant mixture 26 is being held the receiving vessel. The excess nitrite and acid forms N2O3, which then bubbles out of the reactant mixture 26, thus removing the excess nitrite as a potential impurity in the final product.


Looking at the table of impurities in that patent NaNO2/NaNO3 are the main impurities I guess.

So since this method uses the same reactants:P , if using the batch method with nitric acid it should be purified like this right?: 2HNO3 + 2NaNO2 → N2O3 + 2NaNO3 + H2O adding HNO3 until bubbling stops?

Since they use the end product to synth BNCP directly I assume the NaNO3 doesn't play a big role? like for example by the addition of AgNO3 solution?

Can anyone tell if the extraction method with acetone is sufficient to remove the NaNO3 impurity ? I did a batch with CUNT method years ago and didn't find many residu when i did acetone extraction on evaporated NaNT solution left after CuO removal step.

dettoo456 - 30-11-2022 at 10:51

@magneet There shouldn’t be any (if there is it’d be negligible) NaNO3 after Acetone extraction. The NaNTz has good solubility compared to the NaNO3 in Acetone; vice-versa with H2O. If you need a really pure product then routing through with AgNTz can work.

B(a)P - 8-12-2022 at 15:47

Some 5,5'-azotetrazolate salts, via double displacement of sodium 5,5'-azotetrazolate.
The cadmium salt was attempted, the reaction failed as the pH of the cadmium nitrate solution was too high or contained too much dissolved NO2 and the 5,5'-azotetrazolate decomposed.
The ammonium salt was attempted, the reaction failed to produce a precipitate and when taken to dryness decomposed.




PXL_20221208_225056827.jpg - 3.2MB

Etanol - 6-2-2024 at 10:38

Is it normal that the wet Ag nitrotetrazolate does not explode from the fire, but only crackles?
Is it permissible to store AgNTz for 1-2 years in direct contact with PETN, ETN, aluminium, NiCr alloy?
Can AgNTz be recrystallized from water ammonia? Will sensitivity decrease after recrystallization?
Is the stability of AgNTz to light lower or higher than that of AgN3?

B(a)P - 6-2-2024 at 11:18

Quote: Originally posted by Etanol  
Is it normal that the wet Ag nitrotetrazolate does not explode from the fire, but only crackles?

Yes and if you heat it indirectly it will detonate after a short period of time, I guess once it has lost enough water.

Quote: Originally posted by Etanol  
Is it permissible to store AgNTz for 1-2 years in direct contact with PETN, ETN, aluminium, NiCr alloy?

It is storage stable for at least 1 year against copper and aluminium, I have not tried the others you mention.

Quote: Originally posted by Etanol  
Is the stability of AgNTz to light lower or higher than that of AgN3?

I have not tried a comparison to AgN3. It is similar to silver fulminate. In indirect sun light it will decompose within weeks to months.

Etanol - 6-2-2024 at 15:27

Quote: Originally posted by B(a)P  

It is storage stable for at least 1 year against copper and aluminium,

Thank you.
More questions.
Is AgNTz stable to hydrolysis in boiling water? In water with a temperature of 80C?
Is the cream color normal for AgNTz?
Which bulk density is normal for AgNTz?
What is the maximum density when pressing with hands?
Quote: Originally posted by Etanol  

Can AgNTz be recrystallized from water ammonia?

Checked: Yes, perhaps.

[Edited on 6-2-2024 by Etanol]

B(a)P - 7-2-2024 at 02:33

Quote: Originally posted by Etanol  

Is AgNTz stable to hydrolysis in boiling water? In water with a temperature of 80C?

I have not tried, but have seen it reported that it is not susceptible to hydrolysis.
Quote: Originally posted by Etanol  
Is the cream color normal for AgNTz?

Not in my experience, maybe slightly off white though.
Quote: Originally posted by Etanol  
Which bulk density is normal for AgNTz?

I have not measured this nor can I find any reference for it.
Quote: Originally posted by Etanol  
What is the maximum density when pressing with hands?

I have not measured maximum density, but note that using a press it will easily dead press.

Etanol - 8-2-2024 at 12:33

More questions
Is it possible to replace CuCl2 => CuSO4 in the synthesis of DBX-1 with ascorbate?
Is it permissible to store DBX-1 for 1-2 years in direct contact with PETN, ETN, aluminium, NiCr alloy?
Can DBX-1 be recrystallized?

dettoo456 - 8-2-2024 at 15:52

You can probably swap CuCl2 for CuSO4, but you need to reduce the active Cu species to Cu 1, not Cu 2 in any case for the synthesis to work.

DBX-1 likely cannot be recrystallized, simply due to its insolubility, same as AgNTz (which isn’t actually soluble in Aq NH3).

It is likely compatible with PETN, less so with ETN (because of ETN’s inherent instability) and I cannot vouch for its compatibility with Al or Ni-Cr.

If you want a good det train, just use loose AgNTz, loose PETN, and slightly pressed PETN in a brass sleeve.

AgNTz IS NOT COMPATIBLE WITH ALUMINUM THOUGH!

[Edited on 8-2-2024 by dettoo456]

B(a)P - 8-2-2024 at 18:40

Quote: Originally posted by dettoo456  


AgNTz IS NOT COMPATIBLE WITH ALUMINUM THOUGH!



It is interesting that you say this, I have tested this by placing a small sample into an aluminium tube for over 12 months. At the end of the test, there was no obvious mark on the metal or any noticeable change to performance. I note that because the sample was so small I was only able to do limited testing - direct flame test and indirect flame test wrapped in foil.

Etanol - 8-2-2024 at 22:37

Quote: Originally posted by dettoo456  
You can probably swap CuCl2 for CuSO4, but you need to reduce the active Cu species to Cu 1, not Cu 2 in any case for the synthesis to work.

Thanks. I'll try it.
Quote: Originally posted by dettoo456  

DBX-1 likely cannot be recrystallized, simply due to its insolubility, same as AgNTz (which isn’t actually soluble in Aq NH3).

The AgNTz is perfectly dissolved in water ammonia and settles back when the ammonia is evaporated and neutralize by diluted acetic acid to pH3 approximately.
Similarly, I recrystallized silver azide and silver fulminate.
But I am not sure with copper.
Quote: Originally posted by dettoo456  

It is likely compatible with PETN, less so with ETN (because of ETN’s inherent instability) and I cannot vouch for its compatibility with Al or Ni-Cr.

I find "DBX-1 – A Lead Free Replacement for Lead Azide":

"Compatibility studies of DBX-1 with a variety of output powders, bridgewire materials and component metals were conducted by both metal coupon and DSC test
methods...Coupon metals include 1100 aluminum, 6061-T6 aluminum, 2029-T3 aluminum, 304 stainless steel, brass and a MK107 gilding metal cup (95 % copper and 5 % zinc). Observations made during exposure of up to 1 year demonstrated no reaction or change in the coupons.

Compatibility testing was also done on bridgewire materials including Tophet C (nichrome), Tophet A (StableOhm 650) and EvenOhm (StableOhm 800) via DSC....Analyses of the various spectra indicated no shift or change in the thermal profile for DBX-1 and demonstrated compatibility of DBX-1 with these materials."
Quote: Originally posted by dettoo456  

AgNTz IS NOT COMPATIBLE WITH ALUMINUM THOUGH!

Hmm, I'll clarify it.

dettoo456 - 9-2-2024 at 09:26

If your AgNTz is dissolving in aq NH3 then it might just be disassociating into something weird. It shouldn’t dissolve.

Maybe liq NH3 might dissolve it but even if the AgNTz is exposed to aq NH3, the most it might do is form an ammonia complex which would still be insoluble.

Here’s the link to the Al comparability paper (it was a PDF but the website converted it for some reason, you can CTRL F ‘aluminium’ to find it): https://apps.dtic.mil/sti/citations/ADC001137

Etanol - 9-2-2024 at 10:08

Quote: Originally posted by dettoo456  
If your AgNTz is dissolving in aq NH3 then it might just be disassociating into something weird. It shouldn’t dissolve.

Maybe liq NH3 might dissolve it but even if the AgNTz is exposed to aq NH3, the most it might do is form an ammonia complex which would still be insoluble.

This is weird. I do not remember a single insoluble complex of ammonia and silver.
Quote: Originally posted by dettoo456  

Here’s the link to the Al comparability paper (it was a PDF but the website converted it for some reason, you can CTRL F ‘aluminium’ to find it): https://apps.dtic.mil/sti/citations/ADC001137

I find it in webarchive
https://ia801209.us.archive.org/31/items/DTIC_ADC001137/DTIC...
There is metod (c) in this papier: they prepare AgNTz in ammonia solution then add HNO3 to it precipitate.

Is corrosion reaction
Al+3AgNTZ=>Al(NTz)3+3Ag ?

dettoo456 - 9-2-2024 at 12:35

I think the precipitate forms immediately even in the basic solution and the HNO3 is just to balance pH though I might be wrong.

Etanol - 10-2-2024 at 01:47

It is known that the solubility of CuCl in an aqueous NaCl solution is several times higher than in pure water. Does it make sense to add NaCl before DBX-1 synthesis to obtain a more complete conversion of CuCl to CuNTz-1?

Microtek - 10-2-2024 at 06:15

I would think it likely that AgNTz dissolves in ammonia water, forming the soluble diammine silver complex. This happens with silver chloride. Adding the nitric acid would then bind ammonia as the non-complexing ammonium ion and therefore precipitate the AgNTz by releasing the silver ions from the complex.

dettoo456 - 10-2-2024 at 10:42

Ok, my apologies, I haven’t known the AgNTz to be soluble in anything in my experience but I haven’t tried to recrystallized in NH4OH before.

For me, the ‘crude’ product from metathesis w/ AgNO3 has always been pure enough and fine enough in particle size for any EM use. Though, large crystals of the AgNTz do sound interesting if they can somehow be made.

Etanol - 11-2-2024 at 11:18

Once again, I performed 5-ATZ diazoting with hot method, the solution was evaporated and extracted with acetone.
To verify the fullness of extraction, the remainder was acidified with acetic acid, then CuSO4*5H2O, NaCl and ascorbic acid were added and a reaction similar to the preparation of DBX-1 was carried out.
Quite a lot of light brown substance similar to the DBX-1 was distinguished. But the dried substance does not explode and does not burn. What could it be?

Etanol - 13-2-2024 at 15:22

Wow! The DBX-1 is oxidized by the oxygen of air into Cu(NTZ)2 and CuO?! Fuck!
Why isn’t any article talk about this problem?
I'm disappointed.

2. DBX-1 is soluble in water. Bad, but soluble. It does not settle all even at 10°C.

[Edited on 13-2-2024 by Etanol]

Etanol - 15-2-2024 at 00:26

upd...
Inaccuracy
The DBX-1 is soluble in solution after the reaction.
It is insoluble in distilled water. But it is hydrolyzed in boiling distilled water.
Hydrolysis proceeds faster in NaCl solution. DBX-1 is hydrolyzed completely within 2-3 hours in boiling NaCl solution into a black-green non-explosive solid substance.
foto: hydrolyzation product of DBX-1 in NaCl solution
DBX1hydr.png - 367kB

Water ammoia on air decomposes DBX-1 into black CuO and blue solution.
It seems DBX-1 is soluble in hot DMSO with partial decomposition.
Quote: Originally posted by dettoo456  

AgNTz IS NOT COMPATIBLE WITH ALUMINUM THOUGH!
[Edited on 8-2-2024 by dettoo456]

I read that nitrotetrazolates are reduced by Mg,Zn,Al into aminotetrazolates. I mix recrystallized AgNTZ, Al and dist water at room temperature but I did not see a sign of the reaction within 2 day. Maybe this reaction is very slow or requires impurities.

Is it true that BNCP loses NH3 during long storage in wet air?

[Edited on 16-2-2024 by Etanol]

Etanol - 16-2-2024 at 12:22

If you bring the flame to the (NH4)4[Cu(NT)6], does it fully detonate or is there microdetonation with partial spraying of the powder?

Has anyone prepared MTX-1?

dettoo456 - 16-2-2024 at 20:45

MTX-1 is fine. The prep is easy and gives good yield of product, it does stick on glassware though - during the synthesis.

It forms salts, but the pure MTX-1 on its own is weak, and the salts (Ag & NH4) don’t seem to perform much better.

I’d say it’s not worth your Aminoguanidine; 5-NTz or even 5-ATz complexes perform far better. Plus, MTX-1 doesn’t detonate reliably and has a low Tdecomp.

Etanol - 18-2-2024 at 07:33

Is diazodinitrophenol chemically compatible with AgNT? It attracts its low ignition temperature compared to AgNT.
And MTX-1 + AgNT?

[Edited on 18-2-2024 by Etanol]

dettoo456 - 19-2-2024 at 08:24

I read somewhere that tetrazene & MTX-1 are not compatible with AgNTz, though I don’t remember where (somewhere in some military report).

As for DDNP, it may be compatible but it isnt a great primary on its own. It’s unstable in humid and/or hot environments and too sensitive to ignition.

AgNTz is fine on its own in a detonator. It’s relatively heat stable, storage stable, and its only main drawback is ESD sensitivity. You should want a detonator to be as insensitive as possible, until you send 250V or 1/4” fuse into it, that’s the point.

Etanol - 20-2-2024 at 13:02

Is it possible not to separate the 5-aminotetrazole from the reaction mixture, but immediately diazotize it into 5-nitrotetrazole?

aminoguanidine sulphate+H2SO4+NaNO2=>guanilazide
guanilazide+Na2CO3=(reflux)=>5-aminotetrazole
5-aminotetrazole+H2SO4+2NaNO2=>5-nitrotetrazole
5-nitrotetrazole+Na2CO3 or NH3 =>NaNT or NH4NT
in situ all

[Edited on 20-2-2024 by Etanol]

dettoo456 - 20-2-2024 at 13:57

Yes it’s possible but you’d be reacting a strongly diluted mixture of 5-ATz & Na2SO4 with nitrous acid and even more Na2SO4. Plus, you wouldn’t be able to quantify the yield of your 5-ATz yield to calculate req’d reactant amounts, unless you had a very expensive rxn monitoring setup.

The 5-ATz workup should cost too much in yield, and it’s pretty straightforward. If you are really concerned with yield, just dry out the solids from a 5-ATz synthesis and reflux in anhydrous EtOH for an hour or two to completely extract any available 5-ATz. In my experience though, the crystallization of 5-ATz is consistent enough to disregard a different extraction method.

Or just buy the 5-ATz. Thermo sells it at a pretty reasonable price.

Etanol - 20-2-2024 at 21:36

Quote: Originally posted by dettoo456  
Yes it’s possible but you’d be reacting a strongly diluted mixture of 5-ATz & Na2SO4 with nitrous acid and even more Na2SO4.

It's even good. In the diluted solution, the risk of detonation of diazotetrazole in the second stage is less.
Quote: Originally posted by dettoo456  
Plus, you wouldn’t be able to quantify the yield of your 5-ATz yield to calculate req’d reactant amounts, unless you had a very expensive rxn monitoring setup.

Is it important to determine the yield of 5-ATz? Then an excess of acid and NaNO2 is used to diazotation. I can determine the yield of the final product (5-NTz salt) after aceton extraction.
I am concerned about possible organic impurities after the first stage.
Quote: Originally posted by dettoo456  

If you are really concerned with yield, just dry out the solids from a 5-ATz synthesis and reflux in anhydrous EtOH for an hour or two to completely extract any available 5-ATz. In my experience though, the crystallization of 5-ATz is consistent enough to disregard a different extraction method.

Thanks

[Edited on 21-2-2024 by Etanol]

Etanol - 22-2-2024 at 11:28

Quote: Originally posted by dettoo456  

AgNTz IS NOT COMPATIBLE WITH ALUMINUM THOUGH!
Quote: Originally posted by B(a)P  

It is interesting that you say this, I have tested this by placing a small sample into an aluminium tube for over 12 months. At the end of the test, there was no obvious mark on the metal or any noticeable change to performance. I note that because the sample was so small I was only able to do limited testing - direct flame test and indirect flame test wrapped in foil.


Quote: Originally posted by Etanol  

I read that nitrotetrazolates are reduced by Mg,Zn,Al into aminotetrazolates. I mix recrystallized AgNTZ, Al and dist water at room temperature but I did not see a sign of the reaction within 2 day. Maybe this reaction is very slow or requires impurities.


The recrystallized AgNT was stored 8 days at room temperature in a mix with distilled water and aluminum foil. During this time, a few gas bubbles formed and the sample became similar in color to the powder of metal silver. However, the dried sample worked as well as freshly prepared AgNT. The Al-foil has not changed.

On the contrary, wet magnesium reacts very quickly, in minutes, into grey-black powder.

[Edited on 22-2-2024 by Etanol]

[Edited on 22-2-2024 by Etanol]

dettoo456 - 22-2-2024 at 17:28

It might indeed be fine to store with Al, I just saw that the old report I linked advised against it, citing quick decomposition.

I haven’t carried out any tests personally, so store it at your own risk.

B(a)P - 22-2-2024 at 18:42

Quote: Originally posted by Etanol  

The recrystallized AgNT was stored 8 days at room temperature in a mix with distilled water and aluminum foil. During this time, a few gas bubbles formed and the sample became similar in color to the powder of metal silver. However, the dried sample worked as well as freshly prepared AgNT. The Al-foil has not changed.



Thank you for sharing your findings. That you had a reaction when water was involved indicates to me there is an incompatibility. So maybe it is ok to use aluminium as a cavity liner, so long as it is not stored. Seems to me though aluminium is best avoided in this application.

Etanol - 2-3-2024 at 00:33

A simple way to extract nitrotetrazole for NH4NT

Add 15-20%-H2SO4 into NaNT*4H2O to pH=2...1
Heat a little to completely dissolving
Add 4-5 volumes of isopropyl alcohol, shake
Wait
Solid sodium sulfate settled. Transparent yellow nitrotetrazole solution should be assembled with a pipette and neutralized by water ammonia, then dried.
What impurities can remain in the product with such an extraction?

Etanol - 3-3-2024 at 00:49

Why is it recommended to recrystallize BNCP from 1% HClO4, not water NH3? This is a base complex. Acid should decompose it into NH4ClO4, NH4NT, Co(NT)2OH, Co(ClO4)2OH, Co(OH)3 etc.

[Edited on 3-3-2024 by Etanol]

dettoo456 - 3-3-2024 at 09:18

The nitrotetrazole ligands are not strongly coordinated, and amines will take their place if too much base is applied. HClO4 at such low concentrations likely wouldn’t mess with the already acidic nitrotetrazole ligands.

Just speculation though; I’m not an inorganic chem wiz.

Etanol - 4-3-2024 at 02:48

Spontaneous detonation of lead 5-nitrotetrazolate!

It seems I understood why there is no mention of lead nitrotetrazolate Pb(NT)2.
There is only a short message of the salt Pb(OH)NT, which they say it does not have initiating properties.

I tried to make about 0.5 grams of Pb(NT)2 like Pb(N3)2.
2NaNT*4H2O+Pb(NO3)2=>Pb(NT)2+2NaNO3+8H2O
I prepared diluted solutions of NaNT*4H2O and Pb(NO3)2 in distilled water and added 2 drops of acetic acid to NaNT to get Pb(NT)2 rather than Pb(OH)NT.
However, when I mixed the solutions together, the precipitate did not fall out.
Then I put a plastic cup with a solution on a hot pipe of water heating for evaporation.
In the middle of the night, I woke up when I heard strange crackles.
After a few seconds, an explosion occurred, which tore the cup and threw it off the pipe.
However, not all the substance detonated. Most of the substance was smeared in a cup, sprayed with drops and froze with a light yellow crust on the pipe.

At first, I took polycarbonate glasses, then I took a piece of substance from the cup and tried to break it and burn it. But it did not explode.

Then I tried to remove the yellow crust from the pipe with a wooden stick. There was another strong explosion, from which a ringing in the ears appeared!

Summarizing: Pb(NT)2 is well soluble in water and cannot be obtained in pure form.
It seems, Pb(NT)2 forms a non-explosive (or difficult explosive) hydrate, which loses water at elevated temperature.
However, water-free lead nitrotetrazolate Pb(NT)2 is hypersensitive as NI3 and is able to explode spontaneously when dried.

[Edited on 4-3-2024 by Etanol]

dettoo456 - 4-3-2024 at 08:09

A couple of months ago I tried to prepare the Lead salt of 3-Nitro-1,2,4-triazole and got the same sort of thing you mentioned - although the Lead salt was not very energetic. It was prepared from simple metathesis of sodium 3-nitro-1,2,4-triazolate w/Pb(NO3)2 but the product only crystallized out of the solution after around 2 weeks.

IMG_1600.jpeg - 1.8MB

Etanol - 4-3-2024 at 09:23

Quote: Originally posted by dettoo456  
A couple of months ago I tried to prepare the Lead salt of 3-Nitro-1,2,4-triazole and got the same sort of thing you mentioned - although the Lead salt was not very energetic. It was prepared from simple metathesis of sodium 3-nitro-1,2,4-triazolate w/Pb(NO3)2 but the product only crystallized out of the solution after around 2 weeks.


It is interesting. But I have no desire to continue experiments with Pb(NT)2 after the incident.
It is strange that the compounds of lead and tetrazols are so sensitive when azides of lead and silver have almost identical properties. My colleague had a sudden explosion when he tried to assemble a dry lead azotetrazolate from the filter a long time ago.

There is another unpleasant discovery.
It seems, the green primary explosives of a row (NH4)n-2Me(NT)n*(H2O)4-n do not have a constant formula and easily lose NH4NT when washing water.
I tried to prepare the complex (NH4)2Cu(NT)4*2H2O, but I used a more diluted solution than the leadership requires. When I cooled the mixture in the ice, filled, washed with water and dried it, I received only 62% of theoretical mass (NH4)2Cu(NT)4*2H2O.
However, I am sure that I have not lost so much substance because I collected the entire solution and it was almost colorless.
62% of the theoretical mass of (NH4)2Cu(NT)4*2H2O is about 100% of theoretical mass of Cu(NT)2*2...4H2O.
Thus, this is just a crystalline mixture of two salts: Cu(NT)2*nH2O and NH4NT.
Disappointment.

Update. It seems, I realized how to get pure double salt (NH4)n-2Me(NT)n*(H2O)4-n. Need to separately prepare copper salt Cu(NT)2.
CuSO4 or Cu(NO3)2 + NaNT =>Na2SO4 or NaNO3 + Cu(NT)2
wash it from Na salts.
Then mix Cu(NT)2 with an excess of an ammonia salt NH4NT solution, heat, mix for a long time, cool. Should’t wash the product with water!

[Edited on 4-3-2024 by Etanol]

B(a)P - 4-3-2024 at 20:08

Quote: Originally posted by Etanol  
A simple way to extract nitrotetrazole for NH4NT

Add 15-20%-H2SO4 into NaNT*4H2O to pH=2...1
Heat a little to completely dissolving
Add 4-5 volumes of isopropyl alcohol, shake
Wait
Solid sodium sulfate settled. Transparent yellow nitrotetrazole solution should be assembled with a pipette and neutralized by water ammonia, then dried.
What impurities can remain in the product with such an extraction?


This is a very nice procedure for the synthesis of ammonium nitrotetrazole, thanks for sharing, I will try it for myself soon. I don't see that there would be any significant contamination.

With regard to your questions on lead nitrotetrazole, I am surprised to hear that it is soluble. I will (cautiously) try it for myself and report back. I wonder if nitric acid is better for the acidification.

Etanol - 5-3-2024 at 02:33

Quote: Originally posted by Etanol  
A simple way to extract nitrotetrazole for NH4NT

Add 15-20%-H2SO4 into NaNT*4H2O to pH=2...1
Heat a little to completely dissolving
Add 4-5 volumes of isopropyl alcohol, shake
Wait
Solid sodium sulfate settled. Transparent yellow nitrotetrazole solution should be assembled with a pipette and neutralized by water ammonia, then dried.
What impurities can remain in the product with such an extraction?


Quote: Originally posted by B(a)P  

This is a very nice procedure for the synthesis of ammonium nitrotetrazole, thanks for sharing, I will try it for myself soon. I don't see that there would be any significant contamination.


upd
Isopropanol pulls a little water and excess sulfuric acid. Therefore, another stage:
Dry dirty NH4NT should be dissolved in hot isopropanol or acetone, filtered.
NH4NT is soluble in hot isopropanole, (NH4)2SO4 is not.

Etanol - 6-3-2024 at 04:09

The article "5-Aminotetrazoles and Silver-based Primary Explosives" provides formulas and names of complexes AgATz*AgClO4 and AgATz*AgNO3, but they describe the syntheses and yields that correspond to the complexes Ag(ATz)ClO4 and Ag(ATz)NO3.
Has anyone tried to add by drops 0.01 mol 5-aminotetrazole hot solution into 0.01mol AgNO3 solution, then cool it? [AgATz*Ag]NO3 or [Ag(ATz)]NO3 will precipitate?
Theoretically, [Ag(ATz)]NO3 is very effective if it exists.

[Edited on 6-3-2024 by Etanol]

dettoo456 - 6-3-2024 at 08:59

See the thread for ‘Exotic Primaries’

Etanol - 10-3-2024 at 01:00

Quote: Originally posted by dettoo456  
See the thread for ‘Exotic Primaries’

Thanks. I find.

Sadness
I did not think that the complexes of row (NH4)nMe(NT)n+2(H2O)4-n are so fragile.
I tried to get a (NH4)4Cu(NT)6 complex from approximately 5-10% solutions, but after cooling with ice, filtering and flushing cold water again received, judging by the mass, the copper salt Cu(NT)2*4H2O with about 10% content of NH4NT.
It is more likely that in a solid form, this series of substances exists as an ordinary mixture of independent salts Cu(NT)2 and NH4NT.
Similarly, I tried to get nickel-ammonia salt in a more concentrated solution. The result is the same.
I don't know how to get these comlexes in pure form :(
It seems AgNT is the only more or less stable and applicable tetrazole as a primary explosive.

[Edited on 10-3-2024 by Etanol]

[Edited on 10-3-2024 by Etanol]

Etanol - 16-4-2024 at 03:53

How to remove 5-ATz from 5-NTz?
5-NTz, 5-ATZ and its Na/NH4 salts are soluble in water, acetone and hot alcohol.

dettoo456 - 16-4-2024 at 11:22

Excess nitrous acid to convert all 5-ATz is likely the easiest way

B(a)P - 16-4-2024 at 12:55

Quote: Originally posted by Etanol  
Quote: Originally posted by dettoo456  
See the thread for ‘Exotic Primaries’

Thanks. I find.

Sadness
I did not think that the complexes of row (NH4)nMe(NT)n+2(H2O)4-n are so fragile.
I tried to get a (NH4)4Cu(NT)6 complex from approximately 5-10% solutions, but after cooling with ice, filtering and flushing cold water again received, judging by the mass, the copper salt Cu(NT)2*4H2O with about 10% content of NH4NT.
It is more likely that in a solid form, this series of substances exists as an ordinary mixture of independent salts Cu(NT)2 and NH4NT.
Similarly, I tried to get nickel-ammonia salt in a more concentrated solution. The result is the same.
I don't know how to get these comlexes in pure form :(
It seems AgNT is the only more or less stable and applicable tetrazole as a primary explosive.

[Edited on 10-3-2024 by Etanol]

[Edited on 10-3-2024 by Etanol]


I am not sure I understand you. Are you saying that AgNT is the only useful primary of all the tetrazoles? Or are you saying AgNT is the only useful nitrotetrazole? Either way I tend to disagree with this statement. Here are just a few examples:
Tetrazoles
5,5' - azoterazolates
bis tetrazoles
hydrazotetrazoles
There are many others less accessible to the amateur, but not out of reach, for example azidotetrazoles

Nitrotetrazoles
A raft of transition metal, ammonium nitrotetrazole complexes

I don't understand the copper complex that you were trying to synthesise. Firstly, wouldn't it have water in it, I don't see how it would be excluded from the complex when you are using it as a solvent? Also wouldn't it be (NH4)2?

Etanol - 16-4-2024 at 16:19

Quote: Originally posted by B(a)P  

Are you saying that AgNT is the only useful primary of all the tetrazoles?

Right
Quote: Originally posted by B(a)P  

Tetrazoles
5,5' - azoterazolates
bis tetrazoles
hydrazotetrazoles
There are many others less accessible to the amateur, but not out of reach, for example azidotetrazoles

5,5' - azoterazolates - small explosive energy
bis tetrazoles - small explosive energy and slow DDT
hydrazotetrazoles - small explosive energy and slow DDT.

May be nitraminotetrazoles and more difficult compounds...I don't know.
BNCP? There is a small hope. I read that not everyone gets good DDT.
May be double salts aminotetrazoles or azoterazolates or bis tetrazoles or hydrazotetrazoles with HNO3 or HClO4. They seem corrosion active and unstable to moisture.
Quote: Originally posted by B(a)P  

Nitrotetrazoles
A raft of transition metal, ammonium nitrotetrazole complexes

Hg(NT)2 is very toxic
Cd(NT)2 is very toxic
Ni(NT)2,Fe(NT)2,Co(NT)2,Cu(NT)2 form strong hydrates in normal conditions, which causes many failures.
Pb(NT)2 - strong hydrates and high sensitive
DBX-1 quickly decomposes in oxygen
Double complex salts NH4NT or NaNT with Cu(NT)2 or Fe(NT)2 or Ni(NT)2 or Co(NT)2 easily hydrolyzed with water into very soluble NH4NT or NaNT and poorly soluble transition metal nitrotetrazolate.
Quote: Originally posted by B(a)P  

I don't understand the copper complex that you were trying to synthesise. Firstly, wouldn't it have water in it, I don't see how it would be excluded from the complex when you are using it as a solvent? Also wouldn't it be (NH4)2?

According to articles (NH4)2[Cu[NTZ]4(H2O)2] is one of the members of the series:
[Cu[NTZ]2(H2O)4]
NH4[Cu[NTZ]3(H2O)3]
(NH4)2[Cu[NTZ]4(H2O)2]
(NH4)3[Cu[NTZ]5(H2O)]
(NH4)4[Cu[NTZ]6]
With a decrease in the number of water, the sensitivity to the flame grows, the percentage of ignition failures becomes less.
Does it make sense to carry out a reaction in ethyl or methyl alcohol without water and rinse the product only with alcohol?

Sometimes I think NH4CuNT etc are not chemical compounds but mechanical mix of NH4NT and Cu(NT)*nH2O

[Edited on 17-4-2024 by Etanol]

B(a)P - 17-4-2024 at 02:03

Quote: Originally posted by Etanol  



5,5' - azoterazolates - small explosive energy
bis tetrazoles - small explosive energy and slow DDT
hydrazotetrazoles - small explosive energy and slow DDT.



What is this based on? I have not done much testing on anything other than azotetrazolates and what I have done has been limited, but it did not seem to be that azotetrazolates lacked explosive energy. I would be curious to read any references you have on these compounds.

Quote: Originally posted by Etanol  


According to articles (NH4)2[Cu[NTZ]4(H2O)2] is one of the members of the series:
[Cu[NTZ]2(H2O)4]
NH4[Cu[NTZ]3(H2O)3]
(NH4)2[Cu[NTZ]4(H2O)2]
(NH4)3[Cu[NTZ]5(H2O)]
(NH4)4[Cu[NTZ]6]
With a decrease in the number of water, the sensitivity to the flame grows, the percentage of ignition failures becomes less.
Does it make sense to carry out a reaction in ethyl or methyl alcohol without water and rinse the product only with alcohol?



Do you mind sharing the references you are referring to?
Ethanol might be worth a try, it will dissolve the copper nitrate, I don't know what ammonium nitrotetrazole is soluble in other than water. Or perform the reaction at -40C with liquid ammonia as the solvent :D

dettoo456 - 17-4-2024 at 08:06

The 5,5’-Azobis(tetrazolates) are hygroscopic (at least the Na, K, & Ag salt) and the dry salts (of Na, K, Ag, or transition metals) are too sensitive to be practically useful.

I’d tend to agree with Etanol; IMO AgNTz is the only really practical tetrazole. BNCP is alright in terms of performance and sensitivity but requires a mildly complex synthesis, CuNTz is too sensitive to oxidation back to Cu(ii), and the secondaries like TKX-50 are waaaay to expensive to produce on a reasonable scale.

The (Ag2)5-ATz NO3 could be useful but has a wonky preparative method that hasn’t really been replicated well and it could be too labile to degrade to Ag metal over time.

Etanol - 17-4-2024 at 10:27

Quote: Originally posted by B(a)P  
Quote: Originally posted by Etanol  

5,5' - azoterazolates - small explosive energy
bis tetrazoles - small explosive energy and slow DDT
hydrazotetrazoles - small explosive energy and slow DDT.


What is this based on? I have not done much testing on anything other than azotetrazolates and what I have done has been limited, but it did not seem to be that azotetrazolates lacked explosive energy. I would be curious to read any references you have on these compounds.


I tested copper 5,5’-azotetrazolate and 5,5’-Bis-tetrazolyl-hydrazine.

According to the literature, сopper azotetrazolate is the only non-hydrated metal azotetrazolate and therefore the strongest. However, despite the fact that it is able to detonation in the smallest quantity, it seemed to me less brisant than PVA Lead Azide.
Perhaps I am mistaken and the difference is caused by the low bulk density of сopper azotetrazolate compared to PVA LA. I did not measure the mass, but measured it by volume.
In addition, I was afraid to press dry сopper azotetrazolate because it is more sensitive than silver fulminate. It is impossible to work with this in dry form. Maybe I can compress it with alcohol and conduct a correct comparison.

5,5’-Bis-tetrazolyl-hydrazine, Dihydrazinium 5,5’- azotetrazolate and similar substances saturated with hydrogen without oxygen, despite the high enthalpy, do not detonate from fire, but only flare up. Thus, it is not primary explosive.

Energy is my assumption based on their formulas and bonds energies. I could be wrong.

Are you prepare iron 5,5’-azotetrazolate?
Quote: Originally posted by B(a)P  

Quote: Originally posted by Etanol  


According to articles (NH4)2[Cu[NTZ]4(H2O)2] is one of the members of the series:
[Cu[NTZ]2(H2O)4]
NH4[Cu[NTZ]3(H2O)3]
(NH4)2[Cu[NTZ]4(H2O)2]
(NH4)3[Cu[NTZ]5(H2O)]
(NH4)4[Cu[NTZ]6]
With a decrease in the number of water, the sensitivity to the flame grows, the percentage of ignition failures becomes less.
Does it make sense to carry out a reaction in ethyl or methyl alcohol without water and rinse the product only with alcohol?


Do you mind sharing the references you are referring to?
Ethanol might be worth a try, it will dissolve the copper nitrate, I don't know what ammonium nitrotetrazole is soluble in other than water. Or perform the reaction at -40C with liquid ammonia as the solvent :D


For example

Tetrazole Ring-Containing Complexes (R. Matyáš and J. Pachman, Primary Explosives,
DOI 10.1007/978-3-642-28436-6_9, # Springer-Verlag Berlin Heidelberg 2013

Green primary explosives: 5-Nitrotetrazolato-N 2 -ferrate hierarchies
My Hang V. Huynh*, Michael D. Coburn*, Thomas J. Meyer †‡ , and Modi Wetzler

US2006030715 Complex Nitrotetrazole Primary Explosives

and Engager's articles

I prepared NH4NT, Cu(NT)2(hydrate), Ni(NT)2(hydrate) and tried to prepare double salts NH4-Cu and NH4-Ni several times. I noticed the positive effect of NH4NT, but could not bring its content to theoretical.

[Edited on 17-4-2024 by Etanol]

dettoo456 - 17-4-2024 at 10:38

Here’s another reference to the Cu 5-NTz Amine complex:

[Edited on 17-4-2024 by dettoo456]

Attachment: Less Sensitive 5-NTz Salts.pdf (551kB)
This file has been downloaded 339 times

B(a)P - 17-4-2024 at 12:18

Quote: Originally posted by Etanol  


According to the literature, сopper azotetrazolate is the only non-hydrated metal azotetrazolate and therefore the strongest. However, despite the fact that it is able to detonation in the smallest quantity, it seemed to me less brisant than PVA Lead Azide.
Perhaps I am mistaken and the difference is caused by the low bulk density of сopper azotetrazolate compared to PVA LA. I did not measure the mass, but measured it by volume.
In addition, I was afraid to press dry сopper azotetrazolate because it is more sensitive than silver fulminate. It is impossible to work with this in dry form. Maybe I can compress it with alcohol and conduct a correct comparison.

5,5’-Bis-tetrazolyl-hydrazine, Dihydrazinium 5,5’- azotetrazolate and similar substances saturated with hydrogen without oxygen, despite the high enthalpy, do not detonate from fire, but only flare up. Thus, it is not primary explosive.

Energy is my assumption based on their formulas and bonds energies. I could be wrong.

Are you prepare iron 5,5’-azotetrazolate?

[Edited on 17-4-2024 by Etanol]


I didn't realise the silver azotetrazolate salt was a hydrate. I agree that they are generally very sensitive.
I have not tried the iron salt.

Thanks very much for the references Etanol and dettoo456.

Etanol - 17-4-2024 at 12:21

Quote: Originally posted by dettoo456  
Here’s another reference to the Cu 5-NTz Amine complex:
[Edited on 17-4-2024 by dettoo456]

Thanks for the idea, but it seems to be a bad prymary with long DDT.
I dissolved Cu(NT)2*nH2O in hot water-ammonia mix. The result was a beautiful transparent blue solution. Then I cooled it, I collected blue shiny crystals and dried it.
However, from the fire, the substance only burns with small flashes and stop without detonation.
It looks like wet NH4NT or hexaaammine nickel perchlorate properties.
Crystals muddy. It seems that they consist of two phases.
Quote: Originally posted by B(a)P  

I didn't realise the silver azotetrazolate salt was a hydrate. I agree that they are generally very sensitive.

I forgot it. And Hg. Legends go about it's high sensitivity.

I also tried adding a hot ATZ*H2O solution to hot x2 AgNO3 solution without additional HNO3. A white precipitate formed. The pH of the solution decreased to 1.5! The dried substance only burns, but does not explode.
Quote: Originally posted by dettoo456  
If you are really concerned with yield, just dry out the solids from a 5-ATz synthesis and reflux in anhydrous EtOH for an hour or two to completely extract any available 5-ATz. In my experience though, the crystallization of 5-ATz is consistent enough to disregard a different extraction method.

5-ATz is soluble in hot dry acetone and EtOH bad: c.a. 6g/100g of hot acetone and 3.5g/100g of hot EtOH.
But it soluble in hot water-acetone and water-EtOH mixes.
Na2SO4 is soluble in water-acetone and water-EtOH very bad.

[Edited on 18-4-2024 by Etanol]

Etanol - 19-4-2024 at 09:00

Quote: Originally posted by B(a)P  
Quote: Originally posted by Etanol  

5,5' - azoterazolates - small explosive energy

What is this based on? I have not done much testing on anything other than azotetrazolates and what I have done has been limited, but it did not seem to be that azotetrazolates lacked explosive energy.

I was wrong. The calc explosive heat of copper azotetrazolate is sufficient. Due to the high enthalpy of formation.
I think Ni azotetrazolate is perpective if it does not form hydrates, because it should have similar power but less sensitivity. In addition, Ni does not oxidize in the air unlike Fe(2+)=>Fe(3+).

[Edited on 19-4-2024 by Etanol]

B(a)P - 19-4-2024 at 14:53

Quote: Originally posted by Etanol  
Quote: Originally posted by B(a)P  
Quote: Originally posted by Etanol  

5,5' - azoterazolates - small explosive energy

What is this based on? I have not done much testing on anything other than azotetrazolates and what I have done has been limited, but it did not seem to be that azotetrazolates lacked explosive energy.

I was wrong. The calc explosive heat of copper azotetrazolate is sufficient. Due to the high enthalpy of formation.
I think Ni azotetrazolate is perpective if it does not form hydrates, because it should have similar power but less sensitivity. In addition, Ni does not oxidize in the air unlike Fe(2+)=>Fe(3+).

[Edited on 19-4-2024 by Etanol]


I have previously done some experimentation trying to form Ni azotetrazolate perchlorate, I am still in the process of trying to work out what the product was (eg which hydrate if any and is it a complex or double salt). It has some promising properties, but needs more work before I can report anything meaningful back.

Microtek - 21-4-2024 at 09:38

I have recently experimented with 4-amino-1,2,4-triazole as a ligand for nickel perchlorate. I think it probably forms with two 4-ATrz ligands based on yield. The product is not hygroscopic and very insensitive for this kind of compound. I was not able to get any reaction in the oblique impact test on sand paper (highest setting, 5.5 Joule impact), and I was also not able to set it off with hammer and anvil (though this test is not 100% reliable).
It Does DDT from fuse ignition at the 25 mg level, lightly confined. I haven't tested initiation ability yet. Based on flame tests of samples in Al-foil, it seems very thermally stable.

Etanol - 22-4-2024 at 16:04

Quote: Originally posted by dettoo456  
If you are really concerned with yield, just dry out the solids from a 5-ATz synthesis and reflux in anhydrous EtOH for an hour or two to completely extract any available 5-ATz. In my experience though, the crystallization of 5-ATz is consistent enough to disregard a different extraction method.

Thanks. Acetone is better. Using the standard method, I got less than 50% 5-ATZ*H2O from aminoguanidine bicarbonate, H2SO4 and NaNO2. But by adding extraction I increased the yield to 83% of theory.

I compared Сu 5,5'-azotetrazolate and poorly crystallized AgNT compressed by hand with the same force in plastic tubes on metall plates.
Сu 5,5'-azotetrazolate 0.9g/cc was compacted with alcohol then dried within a day because dry subs is very dangerous.
AgNT 1.25g/cc
Сu 5,5'-azotetrazolate at this density is 2 times weaker than AgNT and much weaker than NAP or PVA-Lead Azide compressed with the same force.

Does anyone know the max density and enthalpy of formation of copper 5,5'-azotetrazolate or some other 5,5'-azotetrazolate to evaluate detonation parameters?

I prepare Ni and Co(II) 5,5'-azotetrazolates from raw Na 5,5'-azotetrazolate. Being placed in a flame or on hot foil, they only crack. That is, microdetonation occurs instead of complete detonation. It looks like these are hydrates.
Both substances are poorly soluble in water, but are very difficult to filter. These are rather colloids than crystals.

Is Ag nitroaminotetrazolate sensitivity acceptable for practical use?

[Edited on 23-4-2024 by Etanol]

Etanol - 24-4-2024 at 16:26

More questions about making BNCP
Quote: Originally posted by snooby  

1. Preparation of [Co(NH3)4CO3]2SO4*3H2O complex. 47g CoSO4*7H2O is dissolved it 125 ml of water and is added to solution of 100g (NH4)2CO3 in 500 ml H2O + 250 ml 25% ammonia solution. Resulted dark violet solution is oxidised by addition of 14 ml of 30% hydrogen peroxide. Solution is allowed to sit for 30 minutes, after that period it is placed on boiling water bath and is evaporated to 300 ml volume. During course of the concentration process, solid ammonium carbonate (25 g) was added in installments. Solution is filtered from unsignificant ammount of precipitated black cobalt oxide and is further concentrated to 200 ml volume. Solution is slowly cooled to room temperature, product precipitates as small deep-red prisms. They are filtered out from the solution and allowed to dry at room temperature. Yield is 16 g of pure product, mother liquer can be further concentated with addition of ammonium carbonate to get more 16 g of complex, but it is less pure.

2. Preparation of [Co(NH3)4CO3](ClO4) complex. 16g of complexed synthesised on first stege is dissolved in 320 ml of water. Solution is filtered and 16g of sodium perchlorate in 40 ml of water is added with stirring. Mixture is cooled on ice (or in freezer) for 3-4 hours. Product precipitates as small, lustrous, sharp violet prisms. Crystalls are filtered off, washed with small ammount of ice cold water and dried at room temperature. Yield is about 14 gramms.

3. Preparation of BNCP. 14g [Co(NH3)4CO3](ClO4) is dissolved in 140 ml 10% perchloric acid, and solution of 26.5g of sodium 5-nitrotetrazolate dihydrate in 450 ml of water is added with stirring. Solution is placed on boiling water bath, and allowed to sit there for 4 hours. Solution is slowly cooled to room temperature and then cooled in freezer to 10°С, precipitated crystalls of BNCP are filtered of, washed with cold water, and recrystallised from 1% perchloric acid. Yield is 12.9g.


How can I check that I have prepared a cobalt-3 compound and not a cobalt-2 or a mixture of both? They are the same color.

How can I be sure that I am getting a [Co(NH3)4CO3](ClO4) precipitate and not a mixture of [Co(NH3)4CO3](ClO4) and [Co(NH3)4CO3]2SO4?

I have CoCO3 for ceramics. Can I use it and NH4ClO4, to immediately prepare [Co(NH3)4CO3](ClO4) without SO4 or NO3 anions ?

Etanol - 28-4-2024 at 05:45

How could you oxidize Cobalt(II) ammine complex into Cobalt(III) with H2O2? I add H2O2 drops and it immediately decomposes with bubbles even 3% concentration.

Etanol - 5-5-2024 at 02:30

Acid strangeness in hot synthesis of 5-NT

To prepare NaNT, I dissolved 0.2 mol of ATz*H2O (prepared from aminoguanidine bicarbonate) in 0.2 mol of 37% sulfuric acid for accumulator and diluted with distilled water to a volume of about 200 ml.
Then I dissolved 0.6 mol of NaNO2 in distilled water, filtered it and diluted it to a volume of 200 ml.
I heated both solutions to 60-70 degrees and added a solution of ATz and H2SO4 to a solution of NaNO2 within 60 minutes.
I took into account the acidity of 5-NT, so I thought that the reaction would go like this:

1)2NaNO2+H2SO4=>Na2SO4+2HNO2
2)ATZ+HNO2=>diazoTZ+H2O
3)diazoTZ+HNO2=>NT+H2O+N2
4)NT+NaNO2=>NaNT+HNO2

Thus, only Na2SO4 and NaNT were left in the solution.
I planned to remove the remains of NaNO2 by adding a new portion of H2SO4, but when I measured the acidity of mix, it was already about pH1!

I did not add new H2SO4, but I stir the mixture for 60 minutes at the same temperature.
Then I began to neutralize a hot mixture of baking soda(NaHCO3) to pH7.
I needed 0.2 mol of NaHCO3!

Where could unaccounted 0.2 mole-equivalent of strong acid come from in the reaction mixture?!

Sir_Gawain - 5-5-2024 at 20:18

Did you end up with a yield of NaNTz? It’s possible the reaction didn’t work and so none of the original acid was consumed.

Etanol - 5-5-2024 at 21:28

Quote: Originally posted by Sir_Gawain  
Did you end up with a yield of NaNTz? It’s possible the reaction didn’t work and so none of the original acid was consumed.

I can say the yield when I evaporate the acetone extract.
The reaction works because a golden NaNT extract in acetone was obtained and earlier I already received NaNT and other nitritetrazolates in this way with 50-60% yield with unknown degree of purity.
But the reaction does not work as in theory, it goes with a large overspending of NaNO2.
I have already allocated about 0.5 grams of green copper aminotetrazolate from the remaining mixture of mineral salts after an extraction and I am afraid that even more unreacted 5-ATZ went into acetone extract.

Etanol - 21-5-2024 at 21:38

Quote: Originally posted by Etanol  
Acid strangeness in hot synthesis of 5-NT

To prepare NaNT, I dissolved 0.2 mol of ATz*H2O (prepared from aminoguanidine bicarbonate) i


Quote: Originally posted by Sir_Gawain  
Did you end up with a yield of NaNTz? It’s possible the reaction didn’t work and so none of the original acid was consumed.


I evaporated acetone, filled the aqueous solution and dried it. Then I once again recrystallized a dry substance from acetone and dried. 32.6 g were obtained presumably NaNT*4H2O (78% of theory). But I'm not sure. Maybe there is an admixture of NaATz.
I read that I do not need to highly alkalize the solution after diasoting. Maybe this will not extract unreacted ATz? Are NaATz and ATz differ in solubility in acetone?

dettoo456 - 22-5-2024 at 05:46

NaNTz seems to be very soluble in Acetone and 5ATz only moderately so. But, the actual nitrosation of 5-ATz should yield almost exclusively the NaNTz, and little 5-ATz should remain afterwards. Are you sure you added the H2SO4/5-ATz to the NaNO2 solution and not the other way around?

You shouldn’t need to adjust pH after the reaction - it can just be evaporated down and extracted with Acetone or a different suitable solvent. There shouldn’t be any excess H2SO4, and any excess HNO2 would simply boil off or decompose.

I’d say a 78% yield is pretty good too; nothing to complain about.

Etanol - 22-5-2024 at 09:27

Quote: Originally posted by dettoo456  
Are you sure you added the H2SO4/5-ATz to the NaNO2 solution and not the other way around?

Yes
I think, due to excess acidity, NaNO2 was spent earlier, so the last ATZ is not diazoted.
3HNO2 <=> HNO3+2NO+H2O
HNO3+NaNO2=>NaNO3+HNO2
Quote: Originally posted by dettoo456  

You shouldn’t need to adjust pH after the reaction - it can just be evaporated down and extracted with Acetone or a different suitable solvent. There shouldn’t be any excess H2SO4, and any excess HNO2 would simply boil off or decompose.

I am afraid to evaporate free NTz solution. I read that it is easily decomposed at 100C and exploding. Therefore, I neutralize it into Na salt, then I evaporate and extract it. I think pH 4...5 will be sufficient.

[Edited on 22-5-2024 by Etanol]

dettoo456 - 23-5-2024 at 05:54

The nitrous acid won’t decompose very fast if you carry out the procedure at a normal pace at the required temperatures.

And yes, evaporating a solution of acidic 5-NTz isn’t advisable, but the 5-NaNTz is able to be heated in solution without any real risk of detonation.

Etanol - 31-5-2024 at 17:15

How sensitive is dry copper diazoaminotetrazolate compared to silver nitrotetrazolate? to copper 55-azotetrazolate? to silver fulminate?

[Edited on 1-6-2024 by Etanol]

dettoo456 - 1-6-2024 at 12:09

I’m not sure what the diazoaminotetrazole you speak of is. But the Cu(ii)-5,5’-azobis(tetrazolate) in the dry form is likely very sensitive. I’d say the same with Silver Fulminate.

AgNTz (in my opinion) is relatively insensitive when damp, exceedingly insensitive as a slurry, and only moderately sensitive when dry (between ETN & LA). The fact that it’s amorphous makes a big difference.

Etanol - 1-6-2024 at 14:03

Quote: Originally posted by dettoo456  
I’m not sure what the diazoaminotetrazole you speak of is.


5,5’-Diazoaminotetrazole H(N4C)-N=N-NH-(CN4)H∗H2O
...There are some patents, proposing salts of diazoaminotetrazole as components of electro-igniter mixtures, and as sensitizers for conventional primary explosives. ..
...Copper salt Cu3(C2N11)2 – amorphous precipitate with an olive-green color, almost
insoluble in water, insoluble in organic solvents. Sensitive to impact and friction, on strong grinding in mortar, only part of product is exploded (whitch was directly below the pestle), explodes from fire, flash point 195-220°С...

Monosodium salt synthesis[2] : 25g of aminoguanidine nitrate is dissloved in 125 ml of warm 12-13% acetic acid, 12.5g of sodium acetate is added and the mixture is cooled to 8-10°С and a solution of 17.5g sodium nitrite in 75 ml H2O is added with stirring over 30-40 minutes. Temperature of reaction mixture must be kept below 12-15°С all times, perfectly around 5-7°С. After addition of sodium nitrite, the solution is taken out from the cooling bath and is allowed to sit at room temperature, soon after that evolution of nitrogen is started, sometimes accompanied by heating up to 25°С.
Aproximately after 12 hours, gas evolution stops and precipitation of product is starts, and is completed after 24 hours.
Precipitated crystals are filtered off, washed with ice cold water acidified with acetic acid and is dried at room temperature.

Copper salt synthesis[2] : 43g of monosodium salt is dissolved in 350 ml of water, with added 23 ml of 25% sodium hydroxide. After monosodium salt is fully dissolved, 350 ml of 10% copper sulphate solution is added slowly with stirring.
Olive-green precipitate is filtered off, washed with water, ethanol, either and dried at room temperature.

dettoo456 - 3-6-2024 at 07:13

Oh, the diazoaminotetrazole actually thermally rearranges to Tetrazene in the reaction with acetic acid in dilute concentrations, and tetrazene (and probably its metal salts as well) are sensitive primaries. Tetrazene also degrades rapidly in storage to 5-ATZ, and off-gases HNO2 & N2.

MTX-1, which is prepared by nitrosation of Tetrazene (so you’d need to nitrosate 5-ATZ to Tetrazene with MeCOOH/NaNO2, isolate the Tetrazene, and then nitrosate again and isolate the MTX-1) is a little more sensitive than Tetrazene, but doesn’t degrade in storage.

MTX-1 is completely insoluble in water, as are its ammonium and silver salts. It doesn’t form salts very easily though, as it’s only mildly acidic and isn’t water soluble.

Both Tetrazene and MTX-1 aren’t very useful though, since they only detonate in strong confinement, are very sensitive, and have such low OB% which contributes to their low heats of combustion (not very useful to mixtures with other EMs in blasting caps).

Etanol - 4-6-2024 at 09:51

Wow, copper 5,5'-diazoaminoterazolate is not high sensitive. It is much less sensitive to impact, friction and sting than copper 5,5'-azoterazolate. At the same time, it has excellent DDT and sensitive to fire. It certainly has brisance and initiating ability. Unfortunately, it is much weaker.

Etanol - 25-6-2024 at 03:25

Quote: Originally posted by Microtek  
I have recently experimented with 4-amino-1,2,4-triazole as a ligand for nickel perchlorate


How about unsubstitute 1,2,4-triazole nickel or copper perchlorate complex?

Microtek - 26-6-2024 at 23:35

No, I haven't tried that. The reason I used the amino substituted triazole specifically, is that I have about a kilogram of that compound. I haven't prepared the unsubstituted triazole.

dettoo456 - 5-7-2024 at 19:00

Since this thread involves 5-NTz and the like, I figured I’d ask here since I couldn’t find much (if any) information regarding the disposal/rendering safe of Nitrotetrazole salts. I’d imagine the tetrazole could possibly be oxidized with NaOCl or Ca(OCl)2 to N2, in a similar fashion to azide disposal, but I’m worried that somehow 5-diazotetrazole may be formed in-situ in some way.

The other alternative I’m looking at is reduction with CaCl2 & Fe shavings to 5-ATz which is environmentally benign. I don’t know if the 5-NTz would need to be freebased (acid added to the whole mixture) to properly reduce though. That’d be cheap, aqueous, and largely shouldn’t present any issues that I can think of. Please advise if you would know of any dangers in that route though, other than the issue of acidic 5-NTz in solution.

Also, AgNTz would need to be converted to NaNTz (for safety and solubility reasons) and I think simple mixing of a dilute slurry of AgNTz w/ NaNO3 should be facile.

If nothing else works, 1lb Ammonal surrounding all of the NTz salts would also probably work, but that’s the least appealing option - especially as the salts would need to be transported far away.

Any advice and/or warnings are appreciated.

[Edited on 6-7-2024 by dettoo456]

Microtek - 7-7-2024 at 00:25

One possibility would be to oxidize it to the N-oxide, and maybe form the ammonium or guanidine salt, see linked abstract. Several of these salts are promising secondaries, and some of them are quite insensitive so if you really wanted to dispose of it, you could just burn it.

https://pubmed.ncbi.nlm.nih.gov/21070031/

Etanol - 1-8-2024 at 10:05

Another attempt to prepare BNCP

Heating less than 10 mg of BNCP (presumably) on 0.1mm aluminum foil led to partial detonation:
Attachment: phpfPJDiC (74kB)
This file has been downloaded 235 times

However, I'm not sure that this is BNCP. Perhaps this is a cobalt(III) nitrotetrazolate.
I did not have sexual perversion with sulfate and carbonate complexes.
I did not recrystallize the subs from perchloric acid.
I took 10 mmol cobalt perchlorate (2), added ammonia and 10 mmol of ammonium perchlorate, oxidized it with a large excess of 3%hydrogen peroxide, then added 20 mmol of sodium nitrotetrazolat and boiled until the smell of ammonia disappears. After cooling, the dark brown substance was filtered, and washed with alcohol.

What should be the solubility of BNCP in water? I almost could not recrystallize the substance from the water. Its solubility is small and slightly grows with temperature.

upd
I added perchlonic acid to pH1!, but the precipitate has not changed.
In addition, I evaporated a filtered solution. A little substance was formed, but it has light-brown color (photo No. 2).

nonBNCP2.jpg - 36kB

A light-brown subs is more explosive than dark-brown. In photography No. 3, I slowly heated 3-4 mg of the subs on the 0.1mm aluminum foil and it detonated like a lead azid.
I do not understand why the complex did not form in these conditions, but cobalt nitrotetrazolat was formed.

nonBNCP2test.jpg - 28kB

Attachment: phpenz565 (74kB)
This file has been downloaded 243 times

[Edited on 2-8-2024 by Etanol]

Etanol - 3-8-2024 at 00:38

I think I realized my mistake.
Maybe this information will be useful to someone.

Cobalt(II) complexes of types [Co(NH3)6](ClO4)2 and [Co(NH3)6](NO3)2 are very unstable: it decomposes into cobalt oxide-hydroxide when the solution is diluted with distilled water at room temperature.
These complexes are highly soluble in water.

Cobalt(III) complexes of types [Co(NH3)6](ClO4)3 and [Co(NH3)6](NO3)3 are more stable: at room temperature, it do not decompose upon dilution or even acidification with perchloric or nitric acid to pH=1 (The color of the solutions does not change after acidification and oxygen bubbles do not form.)
These complexes are soluble in water too. However, it decomposes when heated, forming a precipitate of hydroxides! The solution must not be heated!

Plans:
1 mole of Co(ClO4)2 should be dissolved in excess ammonia at room temperature.
2 moles of NaNT*4H2O or NH4NT should be added immediately. A transparent pink solution is formed.
Add excess 3% hydrogen peroxide drop by drop. The solution becomes darker, brown-red. However, the solution remains transparent when held up to a light.
At room temperature, bubble air through the solution to remove ammonia excess .
Add diluted perchloric acid drop by drop until pH=2...1 on indicator paper.
A yellow-brown precipitate should form.

..Failed again

[Edited on 4-8-2024 by Etanol]

Etanol - 7-8-2024 at 22:45

https://www.youtube.com/watch?v=a60UewomiCg
Thanks for the educational video. I still couldn't prepare BNCP, but I prepare a copper analogue of BNCP - copper(II) triammino-nitrotetrazolato perchlorate [Cu(NH3)3NT]ClO4.
The article lies!
As the author of the video correctly said, this is the base complex. It is formed in excess ammonia. Boiling water and acids decompose it! You can't add acid at the end of the synthesis!
Subs is dark blue crystals that are highly soluble in water. It is easily susceptible to fire. Unconfined, it burns completely, unlike [Cu(NH3)4(ClO4)2. After burning, it leaves a pink coating of metallic copper. Confined in foil, it explodes when heated.
As should be the primary explosive, it detonates from the average force impact with a hammer on a steel plate.

Right way:
CuSO4*5H2O+2NaHCO3=(boil)=>Na2SO4+Cu(OH)n(CO3)m+CO2
Cu(OH)n(CO3)m+2HClO4=>Cu(ClO4)2+CO2
Cu(ClO4)2+NH3(excess)+NaNT*4H2O=>|hot solution->cold->ethyl alcogol|=>[Cu(NH3)3NT]ClO4(settles)+NaClO4(solution)

CuNH3NTClO4.jpg - 39kB

[Edited on 8-8-2024 by Etanol]

Etanol - 9-8-2024 at 13:08

The reason for the failures with BNCP, Cu-NH3-NT-ClO4 and, maybe DBX-1 is the large admixture of 5-ATz in 5-NTz in the latest "hot" synthesis.

[Edited on 9-8-2024 by Etanol]
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