Sciencemadness Discussion Board
Not logged in [Login ]
Go To Bottom

Printable Version  
 Pages:  1  ..  22    24
Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
B(a)P
International Hazard
*****




Posts: 1128
Registered: 29-9-2019
Member Is Offline

Mood: Festive

[*] posted on 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.
View user's profile View All Posts By User
Microtek
National Hazard
****




Posts: 836
Registered: 23-9-2002
Member Is Offline

Mood: No Mood

[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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]
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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 ?
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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?!
View user's profile View All Posts By User
Sir_Gawain
Hazard to Others
***




Posts: 302
Registered: 12-10-2022
Location: Due South of Due West
Member Is Offline

Mood: Way less sad

[*] posted on 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.



“Alchemy is trying to turn things yellow; chemistry is trying to avoid things turning yellow.” -Tom deP.
View user's profile Visit user's homepage View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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?
View user's profile View All Posts By User
dettoo456
Hazard to Others
***




Posts: 205
Registered: 12-9-2021
Member Is Offline


[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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]
View user's profile View All Posts By User
dettoo456
Hazard to Others
***




Posts: 205
Registered: 12-9-2021
Member Is Offline


[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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]
View user's profile View All Posts By User
dettoo456
Hazard to Others
***




Posts: 205
Registered: 12-9-2021
Member Is Offline


[*] posted on 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.
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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.
View user's profile View All Posts By User
dettoo456
Hazard to Others
***




Posts: 205
Registered: 12-9-2021
Member Is Offline


[*] posted on 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).
View user's profile View All Posts By User
Etanol
Hazard to Others
***




Posts: 158
Registered: 27-2-2012
Member Is Offline

Mood: No Mood

[*] posted on 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.
View user's profile View All Posts By User
 Pages:  1  ..  22    24

  Go To Top