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B(a)P
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Quote: Originally posted by Etanol  | | Quote: Originally posted by B(a)P |
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.
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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.
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Microtek
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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.
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Etanol
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| 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.
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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]
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Etanol
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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.
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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 ?
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Etanol
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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.
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Etanol
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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?!
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Sir_Gawain
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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.
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Etanol
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| 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.
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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.
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Etanol
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| 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.
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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?
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dettoo456
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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.
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Etanol
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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.
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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]
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dettoo456
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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.
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Etanol
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How sensitive is dry copper diazoaminotetrazolate compared to silver nitrotetrazolate? to copper 55-azotetrazolate? to silver fulminate?
[Edited on 1-6-2024 by Etanol]
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dettoo456
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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.
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Etanol
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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.
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dettoo456
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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).
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Etanol
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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.
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Etanol
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How about unsubstitute 1,2,4-triazole nickel or copper perchlorate complex?
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Microtek
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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.
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dettoo456
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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]
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Microtek
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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/
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Etanol
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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 85 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).
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.
Attachment: phpenz565 (74kB)
This file has been downloaded 89 times
[Edited on 2-8-2024 by Etanol]
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Etanol
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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]
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Etanol
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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)
[Edited on 8-8-2024 by Etanol]
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Etanol
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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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