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Author: Subject: 5-ATZ(5-Aminotetrazole), the nitrotetrazolate ion and friends
Laboratory of Liptakov
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[*] posted on 8-5-2016 at 12:30






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[*] posted on 8-5-2016 at 16:33


That's a relief to see him gone, spreading misinformation in the energetics section could get people killed!
I noticed a lot of what he said implied that he had physically made certain compounds yet at the same time lacked a basic understanding of those comounds properties. Anyone else think he seemed like a complete poser?
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[*] posted on 8-5-2016 at 16:48


Indeed. I'm surprised he lasted this long. The rant in the prepublication thread was a bad move. He did have an air of arrogance and tried to play everyone for fools
but it was easy to see through. I'm sure He will be back reincarnated though. People like that always seem to like having the final say and can't help themselves. - unless he copped an IP ban that is. Check for similar attitudes and post structures.




Where there is a will
there is a way.

Like many of us i also do Youtube.... AllCheMystery!
https://www.youtube.com/channel/UCWbbidIY4v57uczsl0Fgv7w?vie... Fixed link. You can see it now!
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[*] posted on 8-5-2016 at 20:26


I will give this person a second chance...


Quote:
Certainly, I will need something first, though.

1: Find a print edition of ANY of the several volumes of Tadeusz Urbanski: Chemistry and Technology of Explosives. As you are licensed for explosives chemistry work and have friends and mentors in the art, this will present little difficulty.

2: Take a picture of the book, your right hand on the cover, not obscuring title- And also in field of view, the front page from a (local to your home) newspaper, clearly showing the locality and the same date as this picture's posting date. You need not show your face or any other identifying features, and may wear gloves if you wish.

3: Start a new account under the name: a Nitrogen rich material and post this picture as your first post under that name in the "beginnings" forum, along with your oath to post righteously in the future. I will then IMMEDIATELY restore your posting privileges under your original screen name.

After that, you will post some links or other verifiable references showing your sources of information on ANYTHING in the energetic materials fields you choose to ask questions about.

State your informational sources, and explicitly say " I speculate" or "I have personally observed" as appropriate. In the case of original work, actual lab notes, including some pictures of apparatus, operations and products, along with any test data derived and balanced equations for all reactions.






Quote:
I swear that I will stop bullshitting. It hasn't got me far yet, because everybody else is too experienced to see through it. Now, I have heptanitropentane with photos of explosion. Please don't ban me.





Boom.
The explosion removed the windows, the door and most of the chimney.
It was the sort of thing you expected in the Street of alchemists. The neighbors preferred explosions, which were at least identifiable and soon over. They were better than the smells, which crept up on you.
-Terry Pratchett, "Moving Pictures"

It is essential that persons having explosive 
substances under their charge should never 
lose sight of the conviction that, preventive 
measures should always be prescribed 
on the hypothesis of an explosion.

Marcellin Berthelot - 1892 Explosives and their power - Page 47
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[*] posted on 8-5-2016 at 23:28


Why the local newspaper?
Anyway, I'll do what I can.

I haven't been banned from posting!!




I can't think of a better signature.
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[*] posted on 9-5-2016 at 04:32


Erm. I apologize for that, and have made the needed change. Please proceed as directed above...



Boom.
The explosion removed the windows, the door and most of the chimney.
It was the sort of thing you expected in the Street of alchemists. The neighbors preferred explosions, which were at least identifiable and soon over. They were better than the smells, which crept up on you.
-Terry Pratchett, "Moving Pictures"

It is essential that persons having explosive 
substances under their charge should never 
lose sight of the conviction that, preventive 
measures should always be prescribed 
on the hypothesis of an explosion.

Marcellin Berthelot - 1892 Explosives and their power - Page 47
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[*] posted on 9-5-2016 at 11:09


ROFL



Madness is thinking i'm not drunk.
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[*] posted on 13-5-2016 at 05:12


A Nitrogen rich material may be mere animal byproduct in origin, but that is no shame- a smelly mess in the barn can be a valuable fertilizer on the back 40...



Boom.
The explosion removed the windows, the door and most of the chimney.
It was the sort of thing you expected in the Street of alchemists. The neighbors preferred explosions, which were at least identifiable and soon over. They were better than the smells, which crept up on you.
-Terry Pratchett, "Moving Pictures"

It is essential that persons having explosive 
substances under their charge should never 
lose sight of the conviction that, preventive 
measures should always be prescribed 
on the hypothesis of an explosion.

Marcellin Berthelot - 1892 Explosives and their power - Page 47
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[*] posted on 15-5-2016 at 14:40


I thought I was leading the bullshit in this forum until reading nitrogen rich explosive's posts lol
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[*] posted on 16-5-2016 at 04:52


Quote: Originally posted by DubaiAmateurRocketry  
I thought I was leading the bullshit in this forum until reading nitrogen rich explosive's posts lol

No you are not bullshitting Troll at all!
You usually give good, realistic ideas and references.




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[*] posted on 12-6-2016 at 07:35


1,5-Di(nitramino)tetrazole: High Sensitivity and Superior Explosive Performance


This is an interesting report about a green energetic initiator. The synthesis appears to be complex in comparison with the potassium salt of DDNR which would have similar properties.

I think this energetic tetrazole compound should be compared with the potassium salt of DDNR which is gotten much more easily and economically to see if there is a favorable comparison in properties and performance. The economics for the easier gotten DDNR compound could cause it to be a better choice.

Attachment: Fischer_et_al-2015-Angewandte_Chemie_International_Edition.pdf (1.1MB)
This file has been downloaded 235 times
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[*] posted on 12-6-2016 at 12:02


Was wondering, I've seen very crude calcium cyanamide is available here as fertilizer. If one would be interested in cyanoguanidine: what if you would blend diammoniumsulfate/phosphate salts (very cheap) with the impure fertilzer and add to 40-70 deg C water, filter the solution hot and let the cyanoguanidine precipitate (maybe some calcium as well). Was thinking by some trial and error, mixing in the right proportions and taking into account solubilitites of all components, it could be a very cheap and OTC possibility.

I've also seen some people use the calcium cyanurate route for calcium cyanamide. What exactly is this calcium cyanurate? Ca(Cyanuric), Ca(Cyanuric)2, Ca(Cyanuric)(OH)? If you could make the latter, would there be no loss of cyanic acid during pyrolysis and higher yield? Sorry if this has been explained before

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[*] posted on 12-6-2016 at 13:05


Commercial fertilizer grade cyanamide can be worked up to produce cyanoguandine or 25 Kg bags of pure cyanoguanidine are available as a soil treatment slow release nitrogen but it is moderately expensive, maybe $10 per Kg.

I suggest the UTFSE approach to references on calcium cyanurate as a pyrolysis conversion precursor for calcium cyanamide. Since I gleaned that information from patents and other references....it involves a shortcut for the urea and lime process by jumping to the intermediate in that process that would otherwise be formed in situ in a less pure form. Cyanuric acid is easily made from urea and ammonium chloride or can be obtained commercially as chlorine stabilizer, rendered moderately soluble in boiling water neutralizing with sodium bicarbonate as the disodium salt and further reacted with a solution of calcium chloride to precipitate calcium cyanurate, which will pyrolytically convert entirely to pure calcium cyanamide at a low red heat, if air is excluded. First comes off cyanic acid as the calcium cyanurate decomposes first to calcium cyanate, and then CO2 comes off leaving pure calcium cyanamide.
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[*] posted on 12-6-2016 at 14:26


Fair enough, wasnt aware cyanoguanidine was available as fertilizer, haven't seen it anywhere though. And yes, I've seen sulfuric acid neutralization of calcium cyanamide to produce cyanamide and dicyandiamide (local low pH, expensive), CO2 (Needs rigorous stirring and gassing to complete reaction), acetic acid (expensive, usually low concentration), all producing low yield (IIRC). The synthesis of dicyandiamide from free cyanamide is usually performed under basic conditions. From what I've read preferably ammonia and not strong alkali since the alkaline earth metal salts are not stable from what I've read. So combining all of these, the neutralization of calcium cyanamide with cheap ammonium salts forming strongly insoluble calcium salts (mono-di ammonium phosphates, sulfates or maybe even ammonium or sodium bicarbonate) would possibly yield ammonia and cyanamide, which upon condensing would possibly yield dicyandiamide in high yield and I haven't seen this particular route mentioned before.

I've made cyanuric acid from urea before using a bit of (185-210C) boiling paraffin oil as dispersant (OTC candle oil). IMO, there is no other use for the ammonium chloride than for dilution and to make elimination of NH3 from the viscous melt (which could form amelide and amelidine) more easy. So I was now contemplating the synthesis of calcium cyanurate you posted, starting from 2 moles of NaOH, cyanuric acid and calcium chloride posted here: https://www.sciencemadness.org/talk/viewthread.php?tid=2762, which mentions (HOCN)3 + 2 NaOH + CaCl2 ---> CaH(OCN)3 + 2 NaCl + 2 HOH. Just wondering if that second OH of cyanuric acid is deprotonated completely and solubilities of hydroxide double salt may be causing a basic calcium cyanurate to be formed or even if some complex is formed containing additional sodium. I havent seen any mention of a patent here, nor yields of aminoguandine from someone or analysis of the cyanamide produced. It is not criticizing just curiosity.

[Edited on 12-6-2016 by nitro-genes]
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[*] posted on 12-6-2016 at 15:53


Yeah there was a couple of ways to do the stoichiometry and I described the one I think that applied to an experimental I performed. This linked post should take you to other pages that follow up with other ideas.

http://www.sciencemadness.org/talk/viewthread.php?tid=2762&g...

There was an alternative hypothetical possible I think where perhaps there would not be lost anything but CO2 ...but the more straightforward approach seemed to be just to let one cyanic acid burn off to form the calcium cyanate.

[Edited on 6/13/2016 by Rosco Bodine]
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[*] posted on 19-5-2017 at 07:24


Hey Fellas,

I'm relatively new to the pyrotechnics field, but my education background is in chemistry, namely inorganics, coordination chem, catalysis etc. I'm going to be fairly active in my forays into tetrazole chemistry, mostly in pursuit of blue, smokeless, perchlorate-free comps (the pyro quest for holy grail, I know). I was curious if any of you had delved either:

1) 3,6-dihydrazino-1,2,4,5-tetrazine (DHT); or
2)Triazoloaminotriazinyl-1,2,3,5-tetrazine (TATT) salts

TATT was mentioned by Klapotke/Steinhauser as being investigated by Koppes et al, but they never reported on flame colors of any of the salts, which included Al, Co, Ni, Cu, and Ba. My particular interest in the Cupric complex. However, the current synthesis pathway includes the use of cyanogen bromide which makes me tremble a little at the the thought of using.

DHT has many obvious applications in pyro and Klapotke called it "one of the most promising materials for smokeless colored pyrotechnics". Naturally, I have a few reservations in working with hydrazine, plus DHT has hydrazine functional groups that I'm sure make it toxic as all hell. I'd be interested in any light you guys could shed if you've done any research in this area yourselves.

P.S. Enjoy this awesome new article on the effects of adding NQ to your 5-AT propellant mixes! Cheers

pubs.rsc.org/en/content/articlepdf/2017/ra/c7ra01607g

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[*] posted on 21-5-2017 at 04:16


Quote: Originally posted by ShotBored  
Hey Fellas,

I'm relatively new to the pyrotechnics field, but my education background is in chemistry, namely inorganics, coordination chem, catalysis etc. I'm going to be fairly active in my forays into tetrazole chemistry, mostly in pursuit of blue, smokeless, perchlorate-free comps (the pyro quest for holy grail, I know). I was curious if any of you had delved either:

1) 3,6-dihydrazino-1,2,4,5-tetrazine (DHT); or
2)Triazoloaminotriazinyl-1,2,3,5-tetrazine (TATT) salts

TATT was mentioned by Klapotke/Steinhauser as being investigated by Koppes et al, but they never reported on flame colors of any of the salts, which included Al, Co, Ni, Cu, and Ba. My particular interest in the Cupric complex. However, the current synthesis pathway includes the use of cyanogen bromide which makes me tremble a little at the the thought of using.

DHT has many obvious applications in pyro and Klapotke called it "one of the most promising materials for smokeless colored pyrotechnics". Naturally, I have a few reservations in working with hydrazine, plus DHT has hydrazine functional groups that I'm sure make it toxic as all hell. I'd be interested in any light you guys could shed if you've done any research in this area yourselves.

P.S. Enjoy this awesome new article on the effects of adding NQ to your 5-AT propellant mixes! Cheers

pubs.rsc.org/en/content/articlepdf/2017/ra/c7ra01607g


Thank you for the article.

Such rich nitrogen and endothermic compounds tends to burn with a bright or purple-lilac flame (typical example is cyanogen or diamino-tetrazine).

The effect of the cation will thus be visible as an addition colour only if the burning heat is not too strong (otherwise all will shift to bright light (white/silvery/gold).
Cu(2+) will add some blue-green
Al(3+), Ni(2+) or Co(2+) shouldn't give a specific color
Ba (2+) may give a green color.

Would be interesting to test:
Li(+), Sr(2+) for red color,
Ca(2+) for orange/pink color
and B(3+) or BO3(3-) for green color.




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[*] posted on 24-5-2017 at 05:11


Sorry, I said "flame colors" but meant "flame characteristics". I have an understanding of the color emitters down, with the exceptions of some of the newer, rare earth metal emitters such as yttrium, etc. My concern is more so aimed at the established synthesis pathways: it seems self-defeating for me to be aimed at "green" chemistry, yet use such nasty synthesis components such as hydrazine or cyanogen bromide. I was curious if any of you had synthesized DHT or TATT or if you all had used different pathways. I can post the current
general synthesis pathways for each if that would help.

I would agree, though, that forays into those other color emitters could prove fruitful. I know the Klapotke paper talked about some great red-emission from Sr-DHT and Sr-TATT complexes, but I didnt see anything about B, Li, or Ca. I'll have to let you guys know how the research plays out once my lab is done being built =)
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[*] posted on 25-5-2017 at 11:56


Quote: Originally posted by ShotBored  
Sorry, I said "flame colors" but meant "flame characteristics". I have an understanding of the color emitters down, with the exceptions of some of the newer, rare earth metal emitters such as yttrium, etc. My concern is more so aimed at the established synthesis pathways: it seems self-defeating for me to be aimed at "green" chemistry, yet use such nasty synthesis components such as hydrazine or cyanogen bromide. I was curious if any of you had synthesized DHT or TATT or if you all had used different pathways. I can post the current
general synthesis pathways for each if that would help.

I would agree, though, that forays into those other color emitters could prove fruitful. I know the Klapotke paper talked about some great red-emission from Sr-DHT and Sr-TATT complexes, but I didnt see anything about B, Li, or Ca. I'll have to let you guys know how the research plays out once my lab is done being built =)


You may always post synthetic pathways...for informational purpose and to see evolution of technics upon time...

Be careful...greener explosive is not per se related to greener chemistry...it may but it is not mandatory.
Greener explosive means an explosive that is less dangerous/detrimental to the environment...but on its practical use...and mainly focussing on less remanent toxic compounds and heavy metals like Hg, Pb (Quicksilver and Lead) by reference to old timers detonators/ignitors primaries for ammunitions....

It has little to do with the making/fabrication process...
Maybe to include this into a larger ecological view we should speak of "Greenest explosives" or "Enviro-friendly explosives" instead of "Green explosives".

On the other hand Green Chemistry focuses onto the process of making...but not onto the product...actually it may be possible that the resulting product of a green chemistry reaction is a treat to the environment...thus very toxic, remanant, carcinogen, teratogen, ...




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[*] posted on 26-5-2017 at 05:06


Yeah thats true. In my industry, we speak of green chemistry as being comps that do not release toxic byproducts. For example, I have a composition that would be greatly improved by the addition of oxamide right now, however its evolution of cyanogen during combustion makes oxamide pretty much unusable for most of our comps. At the same time, I personally am concerned with the reactants being safe as well for my own personal wellbeing. I'll post a synthesis pathway later today and see if anyone has some ideas on how to do it differently, even if it adds a few extra steps.
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[*] posted on 29-7-2017 at 10:52


Aminoguanidine from calcium cyanamide and hydrazine sulfate:

Out of curiosity I tried a modification to Engager' s original aminoguanidine synthesis to try and make this synthesis easier and less prone to swings in pH during the simultanous additions of the calcium cyanamide /hydrazine sulfate and sulfuric acid by adding an acetic acid/acetate buffer component. All hydrazine sulfate can be added at once and only calcium cyanamide needs to be added , simplifying the synthesis and make it more suitable to perform using only pH paper to measure pH. Wasn't sure about including the presence of acetic acid/acetate due to possible condensations with hydrazine and aminoguanidine, leading to heterocycle formation, acetylhydrazides and disproportionations to diacetylhydrazides resulting in a loss of hydrazine during the reaction. I suspected though that at this pH/and concentrations , these would represent only very minor side reactions. The aminoguanidine obtained this way dissolved to a clear solution in acid (no calcium contamination) and seems to convert to 5-ATZ hydrate in a normal 74% yield using Thiele method. The only difference noticed during diazotization of the aminoguanidine was that there seemed to be just slightly more gas production (nitrogen, hydrazoic?) and a slightly greenish tint at the end of nitrite additions instead of yellow/orange for the aminoguanidine produced by Engager's method., after refluxing, both solutions were slightly yellow.

Procedure:

Outside and wearing two pair of gloves:

- To a 600 ml beaker was added 400 ml ~10% household acetic acid, 19 grams of NaOH was added at once and stirred to dissolve.
- To the quite warm solution was immediately added 55 grams of hydrazine sulfate and stirred briefly, untill
almost all hydrazine sulfate was dissolved. The pH of the solution tested with pH paper at this point was around 4.
- The beaker was added to a cold water bath (tap water) and allowed to cool down to around 20 deg C.
- 40 gram of calcium cyanamide was weighed out and added in small portions to the acetic acid/hydrazine sulfate solution, while keeping temperature around 20 deg C. throughout the additions. The pH was kept between 5-7. After adding about 20-25 grams of calcium cyanamide, additions of cold 50% sulfuric were needed to keep the pH lower than 7.
- When nearly all calcium cyanamide was added the pH was adjusted to 7 using the last bit of calcium cyanmide. The beaker was covered in plastic wrap and kept steering strongly for 1.5 hours at 20 deg C. The pH was checked every 30 minutes or so and 50% sulfuric sulfuric acid added to keep at 7. The pH didn't seem to increase much further anymore after 1 hour.
- After stirring for 1.5 hours, the pH was measured one more time (this one is most crucial!) and carefully adjusted to a pH of 7.
- The contents of the beaker were transfered to a wide neck , 1 liter erlenmeyer flask,. This was covered with a single layer of plastic wrap. and a 500 ml beaker filled with ice was put on top of the flask to keep air out and all hydrazine in the flask.
- The solution was heated slowly and temperature kept between 80 and 90 deg C for two hours. (150-160 deg C setting on my hotplate)
- Allowed to cool down to 60 deg C and filtered off the calcium sulfate. The filtered off calcium sulfate was added to the beaker again and 100 ml of hot water was added, stir redfor 5 minutes and filtered again. Both filtrates combined, pH adjusted to 6.5-7, (pH after heating was somewhere between 7 and 8) and cooled down to 40 deg C.
- 40 grams of sodium bicarbonate were added in small portions over 15 minutes . The aminoguanidine bicarbonate began to precipitate after only a few minutes. Cooled down to 10-15 deg C overnight and filtered, washed thoroughly with ice cold water and dried for 48 hours, yield 39 grams of aminoguanidine bicarbonate.

The simultaneous addition method gave me 22 grams yield and was a lot more hassle to keep track of the pH and temperature at the same time, overshooting temperature to 45 at one point at a pH higher than the pH paper could tell me. This method seemed advantagous since cyanamide solutions are most stable between pH 3-5, maybe even more acetic acid could be used to a starting pH of 3 and keeping temp down even more would minimize losses even more.
Also, my cyanuric acid was made from urea, I suspect yields were still a lot lower than theoretical since the cyanuric acid may not have been completely pure. Calcium cyanurate also seems to react with CO2 from the air to form calcium carbonate and cyanuric acid, which wouldn't form cyanamide during pyrolysis at 800 deg C. I think it may be advantageous next time to dry the calcium cyanurate ASAP.

[Edited on 29-7-2017 by nitro-genes]
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[*] posted on 29-7-2017 at 14:45


@nitrogene; interesting work. Were you working with homemade calcium cyanamide (Engeger style) or using a commercial product. Commercial 55% calcium cyanamide is now readily available in Europe and dirt cheap.
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[*] posted on 29-7-2017 at 15:41


Not sure how easily other some other triazoles would form when acetic acid/acetate is present during the heating step. From what I've read, acylhydrazides need higher temperatures and anhydrous conditions to form (STUDIES OK THE FORMATION OF 4-AMINOTRIAZOLE DERIVATIVES FROM ACYL HYDRAZIDES, ROBERT M. HERBST AND JAMES A. GARRISON).

I've seen the cyanamide fertilizer bags for sale, just more fun going all the way from urea though. :P Cyanamide was homemade by pyrolysis of calcium cyanurate at 800-1000 deg C. Used a welded 150mm diameter stainless steel container with 5 cm of 20 mm stainless tubing protruding from one end by which it could be filled and emptied. A conically shaped stainless steel weight was placed on top of the 20 mm tubing so that when fired, gasses could escape by lifting the weight up, closing it again when no more gas is produced. Worked nicely and gave abundant amounts of silvercyanamide on testing (can this be used for quantification of purity?). Yield was 90% of theory from calcium cyanurate and got 360 grams calcium cyanamide in total from 2 firings, which is more than I need anyway. The original goal was to make dicyandiamide, but decided a small amount of 5-ATZ would also be nice.
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[*] posted on 31-7-2017 at 17:22


Using the silver cyanamide method can be used to calculate purity. In engagers work he mentioned how he done this. I can't remember exactly where I saw it but it is in there. He used the measurements to calculate the N%.
Your method sounds like it's worth a shot. I have had lowered yield in a few of my AQB preparation attempts due to the PH issues. I have finished my furnace so I can heat the calcium cyanate to the exact temperature needed rather than put it in a fire like I have done previously.

I recently did a synth of CuNTZ this was quite nerve racking since I experienced the micro detonations this time around. Quite scary. I recrystallised the product this time from hot water. The colour difference is clear with the refined product being a sky blue rather than the green. It also seems much more flame sensitive too.
I want to attempt DBX-1 again. The last time I tried I suspect the purity of my starting product NaNTZ was not sufficient to get any product to form. I'm trying to get the best possible start to try again.




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Like many of us i also do Youtube.... AllCheMystery!
https://www.youtube.com/channel/UCWbbidIY4v57uczsl0Fgv7w?vie... Fixed link. You can see it now!
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[*] posted on 1-8-2017 at 13:48


Nice channel on YT, some clean looking EM chemistry video's there! The sythesis of CuNTZ was nice to see, some balls to produce it at this scale though, micro dets. and all. A vid on DBX-1 would certainly be cool as well! :)

Not sure what temperature range is acceptable for the pyrolysis of calcium cyanurate to calcium cyanamide indeed. Since the latter is produced commercially by reaction of nitrogen with calcium carbide at 1100 deg C or so, it would seem that at least the calcium cyanamide itself is reasonably stable at these higher temperatures, although this may be different for the pyrolysis reaction. For the pyrolysis I just used an airblown coal furnace from a hairdryer and a 10 liter old SS waste bin with lid that I dug into the ground for insulation. I did give the pyrolysis vessel some "legs" to keep the calcium cyanurate away from the really hot zone at the bottom of the can (where the air is blown in) and eyeballed for a red to dark-orange colour through a peakhole in the lid. Added a small amount of the calcium cyanamide to an excess of 10% HCl, which dissolved it completely and produced only very little gasses or smell, further did a qualitative test with silver nitrate as Engager desribed. The silver cyanamide does have a very low solubility, even from very dilute solutions of cyanamide and ammoniacal silver nitrate (~less than 0.1% for both) a strong yellow colour is obtained, even though it would probably be rather difficult to use the silver method as a really accurate purity assessment.

Also not sure what the exact purity of the AQB is from the acetate/acetic method. I did test the AQB melting/dec. point and the 5-ATZ of both methods, having roughly (together on hotplate test) same melting point, going from tranlucent to matt white at around 100 deg C, same decomposition temp (right after melting with many small bubbles forming) and similar crystal morphology (long glassy plates). Comparing the more energetic copper(II) salts of both batches would be most conclusive, but right now I have no direct plans for the 5-ATZ anyway, so some time perhaps. I did diazotize about 50 mg of the 5-ATZ (of the simultaneous addition batch) as a 0.7% solution and added some 1:1 hydrazine sulfate/NaOH solution to produce some ditetrazoylhexazadiene, truly amazing stuff but also indicative of how dangerous some of these tetrazoles can be.
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