Sciencemadness Discussion Board - Azides

Bother, I was hoping that wouldn't be the case.

Bubbling through a solution?
I hope you don't wish to use water...NaNH2 is very reactive and dangerous against water and moist air...forming unstable peroxyde explosive crust on NaNH2.

Yes, I'm aware, I was hoping to use some other solvent, but none came to mind. I have no access to NH3, so I suppose that's ruled out rather quickly.

No, I was hoping to find an alternate method of carrying out such a reaction without the dangers of molten sodium amide simply to see if it was doable. Making sodium amide "from scratch" reads sigificantly less dangerous than making hydrazine "from scratch". One of my goals was end to end production of what I use, but it would perhaps be easier for the time being to simply look into what you've suggested.

I'll admit that I used google rather than the search engine, but searching "amide" simply yields every time those 5 letters have been together in that order.... rather unwieldy.

I appreciate the response!

Edit:

Unrelated, but awesome photos Etanol!

[Edited on 25-12-2015 by James Ikanov]

REDOXx - 23-1-2016 at 03:05

I made a few photos of my last lead azide synthesis. Directly after a successful synthesis:

And after 12 hours on the Sun (5mg)

The quality is not so good, but I'll try to do better photos. And the synthesis comes naturally also, but I must first translate it from German and my English is net so good....you know?

Hennig Brand - 1-2-2016 at 09:30

Found a clean copy of a really good reference on azide technology today, "Energetic Materials Vol. 2 - Technology of the Inorganic Azides". I already posted this in the short question / quick answer thread, but I thought it was well worth putting here as well. I attached a pdf of "Energetic Materials Vol. 1 - Physics and Chemistry of the Inorganic Azides", but it is a bit rough and also incomplete.

Attachment: Technology of the Inorganic Azides - Energetic Materials Vol 2.pdf (8.4MB)
This file has been downloaded 3760 times

Attachment: Physics and Chemistry of the Inorganic Azides - Energetic Materials Vol 1.pdf (2.6MB)
This file has been downloaded 1345 times

[Edited on 1-2-2016 by Hennig Brand]

Etanol - 12-2-2016 at 13:14

Hello, why do not you make a AgN3 directly from the N2H4*H2SO4, AgNO3 and NaNO3 in an aqueous solution?
It works without NH3 at a very slow pipetting of NaNO3 into N2H4*H2SO4 / AgNO3-solution at room temperature and vigorous stirring.

From 3.65g N2H4*H2SO4 and 3.8g AgNO3 in 150...200 ml water and 1.95г NaNO2 in c.a. 20 ml was obtained 1,56 г AgN3.
Time of addition was 4 hours. Perhaps, one can do faster.

PHILOU Zrealone - 12-2-2016 at 17:50

Quote: Originally posted by Etanol

Hello, why do not you make a AgN3 directly from the N2H4*H2SO4, AgNO3 and NaNO3 in an aqueous solution?
It works without NH3 at a very slow pipetting of NaNO3 into N2H4*H2SO4 / AgNO3-solution at room temperature and vigorous stirring.

From 3.65g N2H4*H2SO4 and 3.8g AgNO3 in 150...200 ml water and 1.95г NaNO2 in c.a. 20 ml was obtained 1,56 г AgN3.
Time of addition was 4 hours. Perhaps, one can do faster.

If true, it is a very horrible yield...one would expect something closer to 3 gr...

Maybe has it to do with decomposition of N2H4 in contact with Ag(+) and with unsoluble Ag2SO4 coprecipitation...

In books I have a brief mention of AgNO3 and N2H4 yielding directly AgN3; I have tried but only silver mirror and N2 gas.
I guess there is a typo and that it should be AgNO2 and N2H4...

Etanol - 13-2-2016 at 00:18

I just recently heard of such a variation of this method. So it was a trial synthesis.I think the yield can be improved.

N2 stands out at too rapid addition of NaNO2 and with stirring is insufficient.
Reaction of silver mirror going with "free" N2H4 (I did't get the mirror ,it was rather the black suspension of Ag )
N2H4-salt gives the desired product.

By the explosive properties the product is identical to that obtained from KN3 and AgNO3.

PHILOU Zrealone - 13-2-2016 at 06:02

How do you separate AgN3 precipitate from Ag and Ag2SO4 ones in the process?

Etanol - 13-2-2016 at 08:27

If the process goes correctly, cleaning is not required: Ag is not formed. And AgN3 is less soluble than the Ag2SO4, and former falls in the first place.

AgN3
water: 0,01g/100g (100°C)

Ag2SO4
0,79 g/100 g H2O (20 °C)

But just in case I dissolved the product in heated water-NH3 (20%), filtered and evaporated NH3.

Great - 13-2-2016 at 14:04

Apparently AgN3 sensitivity to static electricity is a total bitch, or at least by the accounts of members in the other thread. I plan on using it instead of Lead Azide, so can anyone here accurately compare the two? I've got a good impression of shock sensitivities, but less so for static, heat, light, etc.

Rosco Bodine - 27-3-2016 at 20:12

This video shows one good general method for sodium azide. IMO the toxicity for NaN3 is understated as a generality and for some individuals the LD of NaN3 is likely very much smaller. For some materials there is a fairly indefinite range of LD that can vary for the individual.

Also better to use magnetic stirring for the freebasing of the hydrazine from the sulfate to minimize air exposure.

https://www.youtube.com/watch?v=qOSOXVSFdb0

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cupric azide

Rosco Bodine - 28-4-2016 at 06:26

In an earlier post (linked) it was described the complex or double salt possible to form from as a mixed salt sort of compounding of 1 molecule trimethylamine azide with 2 molecules cupric azide to form red crystals exploding 201 C.

http://www.sciencemadness.org/talk/viewthread.php?tid=1778&a...

On you tube has been found a video where someone has been experimenting with small quantities of cupric azide. Although there are many literature warnings about cupric azide having overt sensitivity and danger, there are reported also investigations that show the material may have usefulness if the dangers are managed by control of crystallization and special techniques, similarly as would be the case for other reportedly sensitive materials such as silver fulminate or the like.

Also I think the complexes of cupric azide may have different properties that could provide improvement and reduce the sensitivity of cupric azide so in spite of the historical bad reputation as would discourage experimentation, with renewed interest in "green" technology materials, it could be that some modification of cupric azide may be found that is useful in spite of the bad reputation historically that has been earned by the neat cupric azide alone, or more often reported as attributable to an uncontrolled formation of unregulated crystals as occurs in situ under the special circumstance of decomposition in storage of lead azide in contact with copper or brass.

The deliberate formation of cupric azide or complexes or modifications by a controlled synthesis may result in a more benign material as the result of conditions being regulated for the formation of crystals having better physical properties that could make the material have some limited usefulness. Experimentation with cupric azide and its possible modifications has been limited due to that being discouraged by the historical bad reputation the material has earned, while full details of all particulars are not found, which leaves it to be a question is such a material in fact worthless due to the reported danger which has not been full described in all particulars.

It may be that some variant or modification of cupric azide could have value and the specifics have not been determined or described with respect to what are the required parameters for synthesis and for usefulness as a specific application.

https://www.youtube.com/watch?v=uZz-CQG9qPY

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NeonPulse - 28-4-2016 at 22:33

It does have a pretty bad rep but I I found the copper II azide to be less sensitive as I first thought.it really is made out to be a monster. That's not saying it is safe but It was still quite spark and impact sensitive but I'm not so sure about friction. I could not get it to fire when I ground a small amount between steel surfaces, but I'm sure if I had of added glass or something else gritty and then rubbed it it would have likely fired. The copper I azide seemed far more sensitive,easily detonating violently even with light taps of the hammer. Some of copper azide complexes do sound interesting and I would like to try some of these if I can find a decent synthesis for them. I know the tetraamine copper azide can be made by running a stream of dry ammonia gas over the Cu 2 azide or by dissolving it in ammonia and then evaporation of the liquid with the blue precipitate being the product. I do know that it does quickly lose the ammonia though and reverts back to copper azide. There's also a lithium/copper azide complex I have read about that sounds interesting too. Lithium azide presents a challenge though without hydrazoic acid, and I'm not sure the synthesis of this is something I'm willing to do. It's possible though to make it in a solution of ether or chloroform but again the volatility... A 10% or less concentration is relatively risk less though

a nitrogen rich explosive - 28-4-2016 at 22:36

Does anyone have any experience with mercury azides?
Given how far to the bottom right mercury is, I think HgAz would be extremely sensitive and very powerful

NeonPulse - 28-4-2016 at 22:54

Yes. I can say that I do. I made Hg azide in tiny amounts in plastic vessels. I used Mercury 1 nitrate as this is supposedly much safer than the 2 salt. It detonates violently with an electric blue/white flash and is very sensitive to both impact and sparks. If made with HgNO3 2 you risk extremely sensitive crystals that can detonate even from falling to the bottom of the solution it's contained in. I have not had a small detonating crystal in the solution I had made.. I have a video HgN3 on the tube.

a nitrogen rich explosive - 28-4-2016 at 23:20

The mercury I nitrate version is extremely stable compared to the II version...
I think that Derek Lowe wrote about it on his blog 'Things I won't work with.'

PHILOU Zrealone - 29-4-2016 at 08:13

Quote: Originally posted by NeonPulse

There's also a lithium/copper azide complex I have read about that sounds interesting too. Lithium azide presents a challenge though without hydrazoic acid, and I'm not sure the synthesis of this is something I'm willing to do. It's possible though to make it in a solution of ether or chloroform but again the volatility... A 10% or less concentration is relatively risk less though

Simply change NaOH or KOH for LiOH in the normal NaN3 or KN3 process from Alkyl nitrite hydrolysis upon contact with hydrazine...

This is interesting lithium n-azidocuprates (n= tris, tetra, penta, hexa,...?)...so some transition metals azide may form (probably because of the pseudohalegen behaviour) such complexes as hexacyanoferrate/-ite...
--> hexaazidoferrate of K?
K3Fe(N3)6
--> hexaazidoferrite of K?
K4Fe(N3)6

[Edited on 29-4-2016 by PHILOU Zrealone]

Rosco Bodine - 29-4-2016 at 22:28

Quote: Originally posted by NeonPulse

It does have a pretty bad rep but I I found the copper II azide to be less sensitive as I first thought.it really is made out to be a monster. That's not saying it is safe but It was still quite spark and impact sensitive but I'm not so sure about friction. I could not get it to fire when I ground a small amount between steel surfaces, but I'm sure if I had of added glass or something else gritty and then rubbed it it would have likely fired. The copper I azide seemed far more sensitive,easily detonating violently even with light taps of the hammer. Some of copper azide complexes do sound interesting and I would like to try some of these if I can find a decent synthesis for them. I know the tetraamine copper azide can be made by running a stream of dry ammonia gas over the Cu 2 azide or by dissolving it in ammonia and then evaporation of the liquid with the blue precipitate being the product. I do know that it does quickly lose the ammonia though and reverts back to copper azide.

I am certain I have seen patents for rimfire primer compositions that deliberately used copper azide so it would seem that under precise conditions for synthesis it is possible to make a form of copper azide that has predictable properties.

I have made the material but it has been 40 years ago and I observed the same low solubility that produces a colloidal precipitate similarly as for lead azide when strong solutions of precursors are reacted.

A better but larger crystalline form can be obtained as a general method where dilute solutions are mixed by special technique, which involves simultaneous addition of the two solutions of precursors, equal diluted volumes containing the amount of theory needed for each precursor being added at equal rate. Metering pumps are ideal but two addition funnels adjusted to a slow equal drip rate can substitute.

I.V. solution bottle setups are ideal for this kind of simultaneous addition, and use the needles immersed into the liquid instead of letting drops fall into the liquid. The drip rates can be visualized in an observation chamber on the manual old fashioned I.V. type, or an infusion pump can be used and the delivery rate is digital display.

Anyway the gradual nature of the addition in a stirred liquid flowing past the tip of a cannula seeping in reactants swept into the current of the stirred reaction will favor larger crystal formation. The outlet is immersed in the current of the swirling mixture, and a capillary with a small opening or a gas dispersion tube like the aquarium bubbler diffusers can also be used as outlets, but the flows have to be established before immersion and diffusers can become clogged if there is not a sufficient flow rate to keep the precipitate completely external and not migrating upstream into and clogging the diffuser.

One of the streams of precursor should be introduced through a tube at a greater depth than the other on the opposite side of the beaker which contains an amount of plain water that is about equal to the sum of the very dilute concentration precursor volumes to be added to the stirred reaction, with slow addition streams and the reaction mixture heated and stirred. Such a scheme should produce larger but still microcrystals that should filter quickly.

What is the limiting size of crystal development that may be a danger zone is unknown.

Anyway if you are experimenting with survivably small quantities and are curious this would be what to look at as interest is what changes with increasing crystal size about the properties.

The more dilute the precursor solutions and the higher the temperature and longer the time of additions into the continuous stirred mixture, the larger the crystals should grow.

The dilutions are pretty extreme that are used for these low solubility product systems where a gradual clouding and gradual crystal development is forced to occur by conditions and method, and by extreme I mean for example a couple of grams of end product forming over many hours in a reaction mixture totaling 4 or 5 liters at completion. If spontaneous detonation at a certain size of crystal development occurs, then of course conditions have to be adjusted to use more concentrated precursor solutions, or lower temperature and faster addition rates, or all in combination.

It is possible to design "unvarying continuous reaction conditions" where the composition of the reaction mixture does not change over the course of reaction and such technique should produce a uniform mesh size of crystal product, but finding what is optimum combination of conditions required is the goal there and will lead to a possibly patentable process for the technician who works up those figures and claims the process as proprietary. If there is a dollar to be made from the work, send me a nickel so I can go buy a clue, as my clue supply seems to be dwindling with age and I have fewer and fewer of them to spare as time works its magic on me

I have been thinking that Cu(N3)2 might be a good candidate component in mixture with p-DDNP or NHN as a kicker for those slower self accellerating materials, maybe to produce a good cheap green energetic initiator mixture.

[Edited on 4/30/2016 by Rosco Bodine]

NeonPulse - 2-5-2016 at 17:05

Rosco, did you have a patent number for that or is it one of them things that " those skilled in the art" type things? Your idea actually sounds like a very sound method and would work very well I think. I had a quick look through some patents and only one I found mentioned using CuN3 in its mixtures but it also said that the crystals were kept small using gum Arabic or dextrin. They never said how the azide was formed though. Maybe making larger crystals of CuN3 is not such a good idea....

Rosco Bodine - 2-5-2016 at 18:50

US5610367 cupric azide rimfire primer
is one patent and there is an application for a center fire primer formulation but I don't see any patent ever actually issued on that

Attachment: US5610367 cupric azide rimfire primer.pdf (760kB)
This file has been downloaded 905 times

Etanol - 28-5-2016 at 13:15

Hi guys. Here is another unusual method of preparation of AgN3 from medical Isonicotinohydrazide (C6H7N3O)

1 mol AgNO3
1,2 mol of C6H7N3O
about 2,2 mol HNO3
1,2 mol NaNO2
distilled water

1.
R-CO-N2H3 (3% solution) + AgNO3+ 2HNO3 = R-CO-N2H3*2HNO3+ AgNO3
(With shortage of HNO3 the reaction goes:
R-CO-N2H3 + 2AgNO3 + 2H2O => R-CO-N2H3*2HNO3 + 2AgOH )

2.
R-CO-N2H3*2HNO3 + AgNO3 + NaNO2 (10% solution, 20-25C, addition for 1 hour+exposure for 20-30 hours in a covered glass) = R-CO-OH*HNO3 + AgN3 +NaNO3 + HNO3 + H2O

Yield is 85-95% of the AgNO3

AgNO3 (unreacted) + NaCl = AgCl + NaNO3

Have a good synthesis!)

[Edited on 28-5-2016 by Etanol]

Rosco Bodine - 28-5-2016 at 15:54

Interesting .....do you have a reference for the synthesis ?

This would tend to support earlier speculations that other hydrazides could serve as useful precursors for azides.

Isonicotinic acid hydrazide CAS 54-85-3

synonyms Isoniazid also Pyridine-4-carboxylic hydrazide

Cas No.： 54-85-3
Molecular Formula： C6H7N3O
Molecular Weight： 137.14
Appearance: White to off-white solid
Molecular Structure：

Etanol - 28-5-2016 at 23:48

Source is the lab journal of my friends

Isoniazid is the most available organic acid hydrazide. The tablets are very difficult to filter. The easiest way is to use solution for injection.
Other hydrazides will probably require different pH and go mit a different rate.

Pb(N3)2 is impossible under these conditions due to reactions:
Pb(N3)2 + 2HNO2 +2HNO3 => Pb(NO3)2 + 2N2O +2N2 +2H2O
HN3 + HNO2 => N2O +N2 +H2O

May be this method also suitable for Cu(N3)2

hissingnoise - 29-5-2016 at 06:32

A note of caution ─ copper azide is dangerous to handle and its prep. is best avoided!

Rosco Bodine - 29-5-2016 at 08:31

Quote: Originally posted by Etanol

Source is the lab journal of my friends

See if you can get the name of that lab journal of your friend, and the issue and page numbers.

The discussion about use of hydrazides as a precursor for azides is something I had speculated in another thread that was off topic there should be imported here. The post where I mentioned first the salicylic acid hydrazide is here linked, but that post needs to stay also with the other thread.

http://www.sciencemadness.org/talk/viewthread.php?tid=389&am...

Note to Bert or other moderator:

Everything from this below linked post and to the end of that thread should be imported to here in this thread
http://www.sciencemadness.org/talk/viewthread.php?tid=389&am...

The reference to salicylic acid hydrazide from the post preceding needs to be available here also in this thread and I will put a note in the pruned thread linking to discussion of the hydrazide and azide here.

[Edited on 5/29/2016 by Rosco Bodine]

PHILOU Zrealone - 29-5-2016 at 10:29

It is not speculation, it is a fact known back to the early 1902...with Curtius

See Google Book: Peptides: Synthesis, Structures, and Applications - Bernd Gutte - p3-4

I have read it elsewhere... as a first method of making NaN3 (as explained by me a little below Rosco's post into Rosco's link)

This is very consistent with the reactivity of Ar-CO-NH-CH2-CO-N3 (hippuric acid azide) being comparable to acid chlorides...
Ar-CO-Cl + H2O --> Ar-CO-OH + HCl
Alk-CO-Cl + H2O --> Alk-CO-OH + HCl
so
Ar-CO-N3 + H2O --> Ar-CO-OH + HN3
Alk-CO-N3 + H2O --> Alk-CO-OH + HN3
And with basic catalyst/media one ends up with carboxylate and azide of the base cation
Ar-CO-N3 + H2O -NaOH-> Ar-CO-ONa + NaN3 + H2O
Alk-CO-N3 + H2O -NaOH-> Alk-CO-ONa + NaN3 + H2O

Rosco Bodine - 29-5-2016 at 18:29

Looking at isonicotinic acid hydrazide the the structure is more correctly

54-85-3.jpg.png - 3kB

https://dailymed.nlm.nih.gov/dailymed/image.cfm?id=156505&am...

a synthetic path from the organic acid methyl ester reaction with hydrazine is shown here

http://intranet.tdmu.edu.te.ua/data/kafedra/internal/pharma_...

PHILOU Zrealone - 1-6-2016 at 04:44

Quote: Originally posted by Rosco Bodine

Looking at isonicotinic acid hydrazide the the structure is more correctly

The structure is exactly the same, simply a mirror image from the horizontal plane

And because the molecule is also of symmetry into the screen plane...the two molecules are superimposable by 180° rotation (you of course need to switch the -CO-NH-NH2 from side by a 180° rotation of the bond to the aromatic ring).
The NH can flip on its own and because of the vicinity of the double link...
O=C-NH- <==> HO-C=N-

[Edited on 1-6-2016 by PHILOU Zrealone]

Rosco Bodine - 1-6-2016 at 13:54

It was the side chain Carbon I was looking at as the difference but it could just be the change in structure for new nomenclature where the missing C is "understood" as I have seen that for other compounds that show the "old school" structure delineated clearly versus the "new math" diagrams that I dislike intensely because of the ambiguous "assumed" C in the side chain

PHILOU Zrealone - 1-6-2016 at 16:13

Quote: Originally posted by Rosco Bodine

It was the side chain Carbon I was looking at as the difference but it could just be the change in structure for new nomenclature where the missing C is "understood" as I have seen that for other compounds that show the "old school" structure delineated clearly versus the "new math" diagrams that I dislike intensely because of the ambiguous "assumed" C in the side chain

I understand now

.
Anyway, the second molecule you gave has stil discrete implicite C atoms for the azaaromatic ring...thus lacking 5 C and 4 H ... so practically even if disliked...we commonly use and abuse

Rosco Bodine - 1-6-2016 at 16:35

Yeah there is a C in the side chain for the new nomenclature structure diagram but normal people can't see it because it is depicted in ninja invisibility mode... so that only a special clairvoyant skilled in the ninja invisibility art will recognize it.

Obviously the "old school" classical structure diagram is more clear and more correct, and evidently the international nomenclature and standards committee are a bunch of out of touch and "innovative" academics with their heads stuck up their asses

And then there's the whole NMR structure library discrepancy versus classical structure proofs for DDNR like Klapotke's group identified. We have an unlikely diazo rearrangement there but nobody seems to be looking at the paradox or anomaly. Just let the computer tell you what it is .....or maybe not!

Maybe somebody should look at that issue huh? Just maybe, ya think.

The old timers just get no respect, bumping along with their old seeing eye dog who can't see either .....looking to find real love

https://www.youtube.com/watch?v=-pwC-NVPc58

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[Edited on 6/2/2016 by Rosco Bodine]

dangerous amateur - 14-10-2016 at 13:18

I'd like to ask another question concerning lead azide.

A description of preparation procedure mentiones growing the lead azide crystals out of a dextrine containing solution.

Afterwards the lead azide is put into a concentrated dextrine solution, filtered an dried.

The lead azide is obviously covered with dextrine on the outside, while in the first step dextrine is enclosed in the azide crystals.
What is the exact use of this second step? A phlegmatising one?

When people talk of dextrinated lead azide, what does that mean, that dextrine was used during the crystal growth, or that dextrine was used afterwards?

Thraxx - 15-12-2016 at 09:03

My azide synthesis experiments:
Exp.Nr.1Azide Na synt.
- Bottle One :
Hydrazine sulfate 30g + 50 ml of IP alc.//+ 9,2g NaOH/-20 min. stirring
+ 9,2g NaOH,stirring 15 min,…decantacion into Bottle Two
+ 20 ml IPalc.,stirring,decantation
Bottle Two: Add to decant.sol of H.hydrate + Ipnitrite 28 ml + 9,2g NaOH prills and let stay for 40 h./The NaOH prills stood undissolved ./
Dilute with cold ethanol ,filtration-problem with voluminous greasy soap,filtered through cloth,after diluted in 100 ml watter ,filtered with problems with the soap and precipitated with 500 ml etanol.There was ,after one day in fridge sufficiant amount of azid crystals.

Exp.nr 2-Azide K synt.- What I wanted ,and what I really did.

Prepare one big beaker 500 ml like (Bottle One) one closable bottle of 500 ml volume (like Bottle Two),one help bottle of 200 ml vol. And two cups for KOH prills.
Prepare ice bath for Bottle One

1 Step: Into help beaker prepare 22 g of KOH diluted in 100 ml of IP alcohol.((unsuccesfully,after 24 h was not dissolved,therefore I prepared dilution of 22 g KOH in ethylalcohol of technical grade.It was yellow-brown thick opaque dilution after 3 h.))

2 Step: Into Bottle One: 50g Hydr.sulf. (0,384 mol) + 90 ml Ipalkohol + 22 g KOH prills for 20 min stirring (( because I used ethanol in first step,I used ethanol in the second step to.And this was mistake,because there built from hydr.sulphate not the thick paste,it was thin slurry ))

3.Step: add + 22 g KOH for second 20 min stirring and waite ====== first decantation into bottle Two
((After addition of second 22 g KOH the slurry even though after two hours decantated sharp,but the sodium sulfate was powder and allowed not to pour the extract of.I thought,that its because watter and therefore I gave there 50 ml of IP alcohol,but it wasnt better and I must use the vacuum .))

4.Step: add + 100 ml IP alcohol - KOH solution from the help beaker ,stirring and wait for 30 min.=====second decantation into Bottle Two.
(( this was not possible,because instead of paste I had slurry which could be only filtered))

5.Step: ad + 35 ml IP alcohol stirring and decant==== into Bottle Two .
(( impossible))

6. Step: Into Bottle Two add 47,6 ml of Ipnitrite .
(( this step was well done and result was nice orange solution,where was after 20 h.in ice bath something formed on the bottom.I hope that not a soap))

[Edited on 15-10-2016 by Thraxx]

PHILOU Zrealone - 15-12-2016 at 15:51

Quote: Originally posted by dangerous amateur

I'd like to ask another question concerning lead azide.

A description of preparation procedure mentiones growing the lead azide crystals out of a dextrine containing solution.

Afterwards the lead azide is put into a concentrated dextrine solution, filtered an dried.

The lead azide is obviously covered with dextrine on the outside, while in the first step dextrine is enclosed in the azide crystals.
What is the exact use of this second step? A phlegmatising one?

When people talk of dextrinated lead azide, what does that mean, that dextrine was used during the crystal growth, or that dextrine was used afterwards?

Dextrine treatment afterwards (without prealable dextrin mediated cristallization) would be of no benefit since the main risk is an increase of inner stress of large cristals (the risk of cristal abnormality is bigger into larger cristals); then the cristals may detonate under the slightest stimulus or spontaneously.
The initial treatment allows for tiny regular cristals and that is the most important for flegmatization/phlegmatisation.

PHILOU Zrealone - 15-12-2016 at 15:59

My azide synthesis experiments:
Exp.Nr.1Azide Na synt.
- Bottle One :
Hydrazine sulfate 30g + 50 ml of IP alc.//+ 9,2g NaOH/-20 min. stirring
+ 9,2g NaOH,stirring 15 min,…decantacion into Bottle Two
+ 20 ml IPalc.,stirring,decantation
Bottle Two: Add to decant.sol of H.hydrate + Ipnitrite 28 ml + 9,2g NaOH prills and let stay for 40 h./The NaOH prills stood undissolved ./
Dilute with cold ethanol ,filtration-problem with voluminous greasy soap,filtered through cloth,after diluted in 100 ml watter ,filtered with problems with the soap and precipitated with 500 ml etanol.There was ,after one day in fridge sufficiant amount of azid crystals.

Exp.nr 2-Azide K synt.- What I wanted ,and what I really did.

Prepare one big beaker 500 ml like (Bottle One) one closable bottle of 500 ml volume (like Bottle Two),one help bottle of 200 ml vol. And two cups for KOH prills.
Prepare ice bath for Bottle One

1 Step: Into help beaker prepare 22 g of KOH diluted in 100 ml of IP alcohol.((unsuccesfully,after 24 h was not dissolved,therefore I prepared dilution of 22 g KOH in ethylalcohol of technical grade.It was yellow-brown thick opaque dilution after 3 h.))

2 Step: Into Bottle One: 50g Hydr.sulf. (0,384 mol) + 90 ml Ipalkohol + 22 g KOH prills for 20 min stirring (( because I used ethanol in first step,I used ethanol in the second step to.And this was mistake,because there built from hydr.sulphate not the thick paste,it was thin slurry ))

3.Step: add + 22 g KOH for second 20 min stirring and waite ====== first decantation into bottle Two
((After addition of second 22 g KOH the slurry even though after two hours decantated sharp,but the sodium sulfate was powder and allowed not to pour the extract of.I thought,that its because watter and therefore I gave there 50 ml of IP alcohol,but it wasnt better and I must use the vacuum .))

4.Step: add + 100 ml IP alcohol - KOH solution from the help beaker ,stirring and wait for 30 min.=====second decantation into Bottle Two.
(( this was not possible,because instead of paste I had slurry which could be only filtered))

5.Step: ad + 35 ml IP alcohol stirring and decant==== into Bottle Two .
(( impossible))

6. Step: Into Bottle Two add 47,6 ml of Ipnitrite .
(( this step was well done and result was nice orange solution,where was after 20 h.in ice bath something formed on the bottom.I hope that not a soap))

[Edited on 15-10-2016 by Thraxx]

You play with too big amounts and that is unsafe...you will injure yourself sooner or later.

Nitrite esters are volatile especially the nitrite ester of ethanol and isopropanol; they are also cardio-vascular/blood pressure modifier like nitrate esters...no headaches?
Best choice is n-butyl nitrite and n-pentyl nitrite...less volatile and less flamably-explosive; allows for higher temperature work and reflux.

Soap? No soap can form...soaps are usually salts of anionic organic acids (usually with a long hydrocarbon chain) like NaO3S-Alkyl/Aryl, LiO2C-Alkyl/Aryl; or salts of cationic alkyl/aryl-amines (primary, secondary, tertiary) like chlorides, bromides, sulfates, nitrates...

[Edited on 16-12-2016 by PHILOU Zrealone]

Thraxx - 15-12-2016 at 23:08

I am careful and timid.These experiments I did on balkony in military gasmask and many pairs of gloves. But despite the fact that I did all ,I am worried about details like touching of places and spots .Cancerogenity of hydrazine is well known and remainders of it are waiting.
After 36 h at -2 to +6 C I heat it under reflux. I heated (boiled)1 h and after I pour there 100 ml ethanol for to help precipitation.Now it is orange solution and on the bottom excluded dark orange liquid layer .Tomorrow I will see what happened.
Sources for these experiments:

I. Video of azide synthesis : https://www.youtube.com/watch?v=qOSOXVSFdb0
II.Video is outgoing from the book : Leonid Lerner : Small Scale Synthesis of Laboratory Reagents with Reaction modeling.
This book ,pg. 118: „…while the solubility of hydrazine hydrate in isopropylalkohol is relatively poor….for this reason ethanol is chosen as a suitable compromiss…while the solubility of hydrazin hydrate in ethanol is greater than 2,5 mol/l….230 ml of ethanolic hydrazine hydrate solution + 26,6 g KOH 85% + 39 g Isopropylnitrate…“

III. Sciencemadness and EWF Synthesis

1) Rosco Bodine (2004)
the hydrazine hydrate freebase which may be obtained from the hydrazine sulfate
by reaction of the solid with solid sodium hydroxide , and the absolute minimum
of added water to form a thick slurry of sodium sulfate crystals in hydrazine hydrate ,
which is taken up in successive portions of methanol . Proper technique and glassware
is needed for reactions involving the freebase hydrazine since it is destroyed
fairly rapidly by exposure to oxygen of the air .
The reaction of a slight excess of isopropyl nitrite with a cold methanol solution
of hydrazine hydrate and slight excess of sodium hydroxide , in a slightly pressurized
reaction flask produces a solid precipitate of pure sodium azide crystals in pretty good yield .
A pressure relieved , sealed glass and teflon reaction flask and addition funnel ,
with magnetic stirrer and an ice water bath is needed for performing the synthesis .

2) Microtec: 2004:
For sodium azide production I use a method which gives hydrazine in alcohol ( from hydrazine sulfate ) with little or no water:
- 1 mol dry HS is placed in a flask along with a suitable amount of anhydrous isopropanol.
- 1 mol of NaOH pellets are added and the contents are triturated with a glass rod until they begin to react, forming a slurry of hydrazine hydrate and NaHSO4. This doesn't mix with the iPrOH, but forms a sticky goo on the glass.
- Another 1 mol NaOH is added which converts the NaHSO4 to Na2SO4 ( and forms a mol of water ) which separates cleanly as a white powder.
I would think that the Na2SO4 is a good enough dessicant to dry out the solution which can then be decanted.
- Another extraction or two with dry iPrOH recovers most of the hydrazine.
This alcoholic solution of hydrazine works well for producing sodium azide with isopropyl nitrite
__________________________________________________
Chemicals:
--------------------------------
NaOH :: mol= 39,99 m.p. =318 C,solubility – watter,glycerol,alkohol ethyl 13,9g/100ml/0C,methyl 23,8g/100ml/0C
KOH :: mol=56,105,m.p. =406 solubility-
--------------------------------
Hydrazine hydrate-:: mol=50,liquid mp= -40mboil.p.=118,5C
Soluble in :watter ,alcohol
solubility in isopropyl alkohol is poor,in ethanol 2,5mol /l
Insoluble in :eter ,chloroform
--------------------------------
Hydrazine sulphate::mol=130,12 solid m.p. 254 C,solubility at watter at 20 C =30g/l or 2,86 /100 ml
Insoluble in alcohol
---------------------------------
Sodium azide NaN3 ::
Insoluble in: aceton,ether ,chloroform,in ethanol at 0C =0,22g/100 ml
soluble in watter : 40g /100ml/10C
---------------------------------
Potassium azide KN3 ::
41g/100ml/0C , 105g/100ml/100C ,
Ethanol at 10C 0,137 g/100ml
----------------------------------
Isopropyl nitrite—density :0,87g/cm3
I)93ml (32%)HCL + 49g(61ml) IP alkohol
II) 45g NaNO2 + 80 ml H2O
Yield: 46,5g IPNitrite(53ml)

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Thraxx - 18-12-2016 at 11:27

Important is,that with the technical ethanol I had yield zero-nothing.the layer on the bottom was brown liquid in orange sollution.
Thiele s method need exact 1 mol free hydroxide for one 1 mol of hydrazine hydrate.No less,no more.If there is more,then is the reaction going to NaNO2 and if less,then the between product ,ethylazid,stay in reaction.(I red)
Exp. Nr.1 was the case with more hydroxide.From isopropylnitrit was NaNO2 and sodium isopropylate and it was the orange "Soap"-solubile in watter and swelling with ethanol to voluminous greasy clot.But azide was there too.
Exp.Nr2 was the same case and then the technical ethanol ,which is dilution of devil know what .
I did Experiment Nr.3 with the same rations as Nr.2,but only with IP alcohol.The reaction was slightly orange in last 6 hours of reaction,which tooke 15 h.Yield -there was something insoluble in acetone.
I allowe me to suggest this procedure of Microtecs method:
less than 1 mol of IPnitrit /89/+extraction of 1 mol of Hydr.sulph./130/(of more than 2x 1 mol of KOH/more than 2x 56/)+ 1 mol KOH /56/(in IPalcohol 14:100) for more than 50 h.
I allowe me to tell,that the method of cold extraction publicate by Microtec is before unpublicate ,therefore original and worthy of patent.

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Is this really it?

TheMrbunGee - 22-12-2016 at 02:14

So In The linked video, you can see Sodium nitrite and Urea mixed (amounts eyeballed, with slightly more urea)

Mix is then heated with direct flame,

Firstly - everything melts, some gas bubbles off (it might be even steam, CO2 and may be some ammonia) and everything solidifies,

Then it melts again, starts fizzing kind of loudly, a lot of Na ions goes in to the flame and finally explodes loudly and sharply!

It does look like Sodium azide, I could not find any real proof for this reaction, just some incomplete rumors about it. What is the equation?

https://youtu.be/VzyWsdWfGUY

[Edited on 22-12-2016 by TheMrbunGee]

PHILOU Zrealone - 22-12-2016 at 09:13

Quote: Originally posted by TheMrbunGee

So In The linked video, you can see Sodium nitrite and Urea mixed (amounts eyeballed, with slightly more urea)

Mix is then heated with direct flame,

Firstly - everything melts, some gas bubbles off (it might be even steam, CO2 and may be some ammonia) and everything solidifies,

Then it melts again, starts fizzing kind of loudly, a lot of Na ions goes in to the flame and finally explodes loudly and sharply!

It does look like Sodium azide, I could not find any real proof for this reaction, just some incomplete rumors about it. What is the equation?

https://youtu.be/VzyWsdWfGUY

[Edited on 22-12-2016 by TheMrbunGee]

Nice bang! Maybe that the iron plated plate under it contributed as a catalyst...Would be nice to test this onto an inert surface like glazed ceramic.

Most probable reaction:
-No azide at all!
-Under the strong heating you get dehydration/condensation of urea into biuret, triuret and finally into melamine (triamino-sym-triazine)
H2N-CO-NH2 + H2N-CO-NH2 --> H2N-CO-NH-CO-NH2 + NH3(g)
H2N-CO-NH-CO-NH2 + H2N-CO-NH2 --> H2N-CO-NH-CO-NH-CO-NH2 + NH3(g)
H2N-CO-NH-CO-NH2 <==> H2N-C(-OH)=N-CO-NH2
3 H2N-CO-NH2 -heat-> (-N=C(NH2)-)3 + 3 H2O

Then urea, biuret, triuret and especially melamine(*) are fuels; while NaNO2 is an oxydizer.
Into the molten state both are intimately mixed at a molecular level and as such may deflagrate/detonate(**) because the average energy of all the molecules is already high due to the preheating/melting... just like trowing an enflamed match into preheated dry wood.

Would be much more interesting to start immediately from melamine...it spares you the heating and evaporation of 3 molecules of H2O.

(*)Melamine can be considered as a trimer of cyanamide H2N-C#N.
Cyanide (and melamine) is a good way to store energy as mutliple C-N double or triple bond.
(**) A typical example is the mix of NaCN and NaNO2 what may deflagrate/detonate when molten.

[Edited on 22-12-2016 by PHILOU Zrealone]

TheMrbunGee - 22-12-2016 at 11:32

I did the reaction on aluminum foil, still exploded! Will glass plate suffice? I will try it!

So I am able to test your theory by heating Carbamide alone, then mixing with NaNO3 and heating them together.. I will also try that!

Strange, that nothing happens if I do the same with KNO3, nothing at all!

EDIT:

Same explosion on a glass!

Carbamide and NaNO2 IS reacting and forming something, because urea alone never solidifies while heating, neither does NaNO2 alone! Really looks like a reaction!

[Edited on 22-12-2016 by TheMrbunGee]

PHILOU Zrealone - 22-12-2016 at 12:07

Quote: Originally posted by TheMrbunGee

Glass plate will be OK but glass resist less than glazzed ceramic towards high temperature differences so the glass may break or explode from internal stress...except if heating is done homogeneously--> on a tiny piece of glass.

NaNO3 might also work with melamine/urea since upon heating NaNO3 turns partially into NaNO2.

Maybe that the melting point is important here to get a good molecular mixing...also NaNO2 is more hygroscopic...so the water of cristallization may dissolve melamine and NaNO2 while heating helping to a better mixing.

I was lazy so I took info from Google-wiki instead of my mineral and organic chemistry books...
Urea:
133°C

Biuret:
190°C (decomp)

Triuret:
? probably also decomp arround 190°C

Melamine:
345°C (decomp)

NaNO2:
271°C
Decomposes above 320-330°C
2 NaNO2 → Na2O + NO + NO2

NaNO3:
308°C
Decomposes above 380°C

KNO2:
440°C (decomp)

KNO3:
334°C
Decomposes from 400°C to O2 and KNO2

In your case the mixing seems optimal thanks to the following factors:
-the low mp of urea
-the water produced by urea transformation into melamine
-the low mp of sodium nitrite (should work also with NaNO3)
-the water from the NaNO2
-the similar decomposition temperature of NaNO2 and melamine

Such melting point behaviour has been observed IIRC by forum member "Dornier 335A" with its detonating energetic whistle mixes of hybrid Na/K chlorate-benzoate salts.

I suspect that one would get such optimum mixing conditions by dissolving the compounds into the minimum quantity of warm water and boil the water off as fast as possible.

[Edited on 22-12-2016 by PHILOU Zrealone]

PHILOU Zrealone - 22-12-2016 at 12:41

Very interesting...this needs further study!

Other speculations:
NaNO2 + reducer --> Na-O-N=N-O-Na (hyponitrite)
or
NO and NO2 from NaNO2 are reacting with the H2N- group from urea or melamine to make diazoniums and since Na2O is present aswel...diazotates (wich are known to be explosive but more stable than anionic diazonium salts).

H2N-CO-NH2 + NO + NO2 --> O=N-NH-CO-NH2 + O=N-NH-CO-NH-N=O
(-C(-NH2)=N-)3 + NO + NO2 --> (-C(-NH-N=O)=N-)3 (or on two of the NH2 or only on one of those)

O=N-NH-CO-NH2 <==> HO-N=N-CO-NH2 <==> HO-N=N-C(OH)=NH
O=N-NH-CO-NH-N=O <==> HO-N=N-CO-N=N-OH
(-C(-NH-N=O)=N-)3 <==> (-C(-N=N-OH)=N-)3

HO-N=N-C(OH)=NH + Na2O --> NaO-N=N-C(ONa)=NH + H2O
HO-N=N-CO-N=N-OH + Na2O --> NaO-N=N-CO-N=N-ONa + H2O
2 (-C(-N=N-OH)=N-)3 + 3 Na2O --> 2 (-C(-N=N-ONa)=N-)3 + 3 H2O

Finally those putative diazo compounds may react onto a NH2 to make a triazene (see benzotriazole formation from ortho-diamines and nitrosation agents like HNO2, Cl-N=O or alkyl nitrite)
H2N-CO-NH2 + HO-N=N-CO-NH2 --> H2N-CO-NH-N=N-CO-NH2
The NH2 may come from urea, biuret, triuret or melamine and the triazene may also make a Na salt because the NH from triazene is acidic.

Last possibilities azides or tetrazoles via obscure pathways...

[Edited on 22-12-2016 by PHILOU Zrealone]

Theoretic - 30-12-2016 at 06:52

Diazonium salts are less likely to be the answer, as they are very unstable things and most decompose spontaneously below room temperature. Urea will isomerise reversibly to ammonium carbamate, the ammonium may protonate the nitrite and the resulting nitrous acid will react with urea and it's condensed derivatives; however diazoniums will be formed only very transiently:
"H⁺" + NO₂^- => HNO₂
HNO₂ + (NH₂)₂CO => [(N₂)CO(NH₂)⁺] => N₂ + NH₂=CO⁺ => polymerisation products (biuret, melamine etc)
Much the same thing will happen after any urea derivative reacts with the transient nitrous acid - transient diazonium and decomposition. Of course ammonia, having given up its proton to nitrite, will react with the nitrous acid faster than anything else, being more nucleophilic than urea etc. This produces the original HN₂⁺ diazonium action.
These reactions release a great deal of heat and gases. Decomposition of urea to ammonium carbamate will release CO₂, water and ammonia, without releasing energy. This will carry away heat, but eventually the diazonium reactions will drive the mixture to deflagration, which transitions to detonation.

PHILOU Zrealone - 30-12-2016 at 09:51

Diazonium salts are less likely to be the answer, as they are very unstable things and most decompose spontaneously below room temperature. Urea will isomerise reversibly to ammonium carbamate, the ammonium may protonate the nitrite and the resulting nitrous acid will react with urea and it's condensed derivatives; however diazoniums will be formed only very transiently:
"H⁺" + NO₂^- => HNO₂
HNO₂ + (NH₂)₂CO => [(N₂)CO(NH₂)⁺] => N₂ + NH₂=CO⁺ => polymerisation products (biuret, melamine etc)
Much the same thing will happen after any urea derivative reacts with the transient nitrous acid - transient diazonium and decomposition. Of course ammonia, having given up its proton to nitrite, will react with the nitrous acid faster than anything else, being more nucleophilic than urea etc. This produces the original HN₂⁺ diazonium action.
These reactions release a great deal of heat and gases. Decomposition of urea to ammonium carbamate will release CO₂, water and ammonia, without releasing energy. This will carry away heat, but eventually the diazonium reactions will drive the mixture to deflagration, which transitions to detonation.

Some diazoniums are quite stable...and isolable dry at ambiant T° and even above without signifiant risks of explosion.

See in Traité de Chimie Organique; Published - under the direction of V Grignard, G Dupont, R Locquin, P Baud - by Masson & Cie - Tome 15: Diazoiques et Azoiques, Triazenes, Tetrazenes,...

A) Diazonium cyanide for example has no salt structure and is fully covalent compound --> Ar-N=N-C#N
B) Diazotates is another class of diazo-salts much stabler compounds than anionic diazoniums salts
Ar-NH-N=O <==> Ar-N=N-O-H
Ar-N=N-OH <==> Ar-N=N(+) + OH(-) (into an acidic medium --> diazoniums)
Ar-N=N-OH <==> Ar-N=N-O(-) + H(+) (into a strongly basic media like Na, K, Li hydroxyde or oxyde --> diazotates)

This last class may be cis- or trans-benzodiazotates...a stable transportable storage form of diazonium...reformed by simple acidification of diluted solutions.

This last class is even present into the alkylic familly with a much increased stability than normal alkylic diazoniums wich are very unstable; sole requisit, the presence of an electron withdrawing group onto the carbon holding the diazo.
-->Typical example is glycine ester...upon diazotation
RO-CO-CH2-NH2 + HO-N=O <--==> RO-CO-CH2-NH-N=O + H2O
RO-CO-CH2-NH-N=O <====> RO-CO-CH2-N=N-OH
The CH2 is "acidic" because of two EWG groups...the (-O-)C=O on one side and the N=N(-O-) on the other side; as such it is more than happy to leave a H(+) that goes away with the terminal OH(-).
As a result you get a diazoacetic ester and water: RO-CO-CHN2
This later diazoacetic ester is hydrolysable by bases like NaOH to generate stable diazoacetates like NaO2C-CHN2 ...
Diazoacetic acid, salts and esters are substances that are stable up to a certain temperature above what they explode or generate strange reactions involving free radicals (alcenic dimerizations, cyclopropane trimerizations, addition of 2 halogens (if present) in place of the N2...)

[Edited on 30-12-2016 by PHILOU Zrealone]

Theoretic - 30-12-2016 at 11:28

A) Diazonium cyanide for example has no salt structure and is fully covalent compound --> Ar-N=N-C#N
B) Diazotates is another class of diazo-salts much stabler compounds than anionic diazoniums salts

These aren't diazonium compounds. They're azo compounds if they're covalent. Diazo compounds aren't diazonium either. Diazonium meant the cations, and those would not build up to any level in that melt, but decompose immediately. For most diazoniums the cation left by the nitrogen departing is not so unstable that the reaction is anywhere near slow. The energy released by N₂ leaving is too great.

[Edited on 30-12-2016 by Theoretic]

PHILOU Zrealone - 30-12-2016 at 11:57

A) Diazonium cyanide for example has no salt structure and is fully covalent compound --> Ar-N=N-C#N
B) Diazotates is another class of diazo-salts much stabler compounds than anionic diazoniums salts

Call them what you want but:
Ar-N=N-C#N is made from diazonium salt and cyanide anion...and is called diazonium cyanide despite it has no charge.
Ar-N=N-ONa is made from diazonium hydroxyde and a strong base...it is not covalent how could it be with Na in it? Again a simple acidification gives the diazonium back...
--> as such structurally speaking both are very closely related to diazoniums...just missing the (+) onto the N2 group.

Azo compounds are more like Alk-N=N-Alk, Ar-N=N-Ar or Ar-N=N-Alk so you are also wrong

That was indeed my point diazonium cation (thus linked to an anion) are much less stable and will not survive into the melt while my related propositions may survive because much more stable...but this remains to study.

[Edited on 30-12-2016 by PHILOU Zrealone]

Theoretic - 30-12-2016 at 18:33

Diazonium cyanides aren't diazonium salts, they have the terminal N bonded to a carbon, and covalently. That's a critical difference, whether it sounds like a diazonium salt or not. And even both ends wouldn't be enough at the temperatures of the melt. Tautomerization would be lightning fast, and as soon as one NH₂ is nitrosated, it is turned into N₂ soon as blink. Nitrosourea doesn't even survive room temperatures, and it's condensed derivatives will hardly fare better.

Marvin - 31-12-2016 at 02:32

Yellow powder produces a sharp sounding unconfined detonation if the melt is heated enough. I personally don't believe this is much more complicated than a solution of nitrate and sulphide/polysulphide. As a solution, the mix is molecular in scale, which is almost as good as having the intramolecular redox reaction that we expect from a detonating substance. The other aspect is that at elevated temperature the bar to detonation is much lower. Even ammonium perchlorate will detonate if hot enough.

If the fuel and nitrite are miscible I'd expect the hot melt to support a detonation.

Thraxx - 5-1-2017 at 12:49

What you think about this method ? :

1.-Hydrazine Sulphate + Ba/NO3/2 == Filtration==
2. Hydrazine nitrate + solution of NaNO2 + HNO3 ==
3. NaOH into baker with reaction 2====NaN3 + NaNO3 + NaNO2

(Step 1 is mentioned in Fedoroff
Step 2 does work wih sulphuric acid.If the solution will have not free nitric ac.,which could destroy azid,then it could does work.
All solutions should be very diluted.)
--------------------------------------------------------------------------------
Stolle´s method (my variation)
13 g Hydrazine sulphate + 12 g Aq NaOH in 26 ml watter + 52 ml IPalcohol + 12 ml IPnitrite
After 24 h filtered and dryied.
Dry product diluted in watter .
I expected,that there is or could be 6,5g NaN3 and a lot of NaHSO4 and Na2SO4 and NaOH too.
Therefore I diluted it im 50ml watter and added there 70 ml technical ethanole.It precipitate-NaN3 together with sulphate.Filtrated ,diluted in 30ml watter.
Mixed with solution of CuSO4 and after longer time there was on the bottom something like white crystals.If there was free hydrazine,then it could be Cu(I)N3,if not,then it will be Cu(II)N3.

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

PHILOU Zrealone - 5-1-2017 at 14:47

Stolle´s method (my variation)
13 g Hydrazine sulphate + 12 g Aq NaOH in 26 ml watter + 52 ml IPalcohol + 12 ml IPnitrite
After 24 h filtered and dryied.
Dry product diluted in watter .
I expected,that there is or could be 6,5g NaN3 and a lot of NaHSO4 and Na2SO4 and NaOH too.
Therefore I diluted it im 50ml watter and added there 70 ml technical ethanole.It precipitate-NaN3 together with sulphate.Filtrated ,diluted in 30ml watter.
Mixed with solution of CuSO4 and after longer time there was on the bottom something like white crystals.If there was free hydrazine,then it could be Cu(I)N3,if not,then it will be Cu(II)N3.

The variation seems like N2H4.H2O + organic nitrite Ester + mineral base (NaOH, KOH or LiOH) method in disguise...because N2H4.H2SO4 + NaOH makes N2H4...

You can't have a lot of NaN3 and NaHSO4 and Na2SO4 and NaOH too...
1°) NaN3 and NaHSO4 is like playing with hydrogen cyanide...very toxic HN3 volatile liquid or gas is formed...
2°) If NaOH is present then NaHSO4 turns into Na2SO4 because the first is a strong base and the second is a quite strong acid.
3°) It is really advisable to have an exces of NaOH when playing with azide because of 1°).

Cu(II) azide (cupric azide) is brown-red and very sensitive explosive even when wet!
Cu(I) azide is white
see Silver, cupric and cuprous azides

Thraxx - 6-1-2017 at 02:56

Thank you for advice about the Na2SO4 and NaHSO4.If there is only Na2SO4,then it could be separate from NaN3 through freeze-Na2SO4 is only 4-5g/100ml at 0C,while NaN3 is soluble ten times more.

Azides from Hydrazine sulphate :
I.Variations of Stolles method without extraction or separating the mixture of sulfate from hydrazine hydrate.On the end of reaction is mixture of NaN3 + Na2SO4 ,which Stolle separate through distillation.

II.-Variations of Thieles method /extraction methods which excluded sulfate from reaction ,like
-IPA -Microtek
-Methanol-Rosco Bodine
-Methanol-Sulphuric acid -pat.GB 76038
-Sodium methoxide -Brauer

III.variations of Curtius method -
neutralisation of distilled aq. hydrazoic acid(azoimid) from mixture alk.nitrite + hydraz.sulph. + sulphuric acid

Thraxx - 10-1-2017 at 05:17

I would like to tell you,that after 12 experiments with IP extract + IPnitrite + hydroxide was my yields of azid only 2,5 g from first experiment ( hydroxid was there in Ethanol and partialy not diluted).In all other cases I produced amorphic yellow material,solubile in watter but recrystalisation with alcohol is not possible it turns into brown liquid solubile in watter and insolubile in alcohol or into nothing.This liquid react with AgNO3,but product is not energetic material.
I am sure,that I did some mistake,but I dont understand it.
Similar reaction is method of Opelkin,which gave Hydrazine hydrate + NaOH (solid? aquous?) + Ethylnitrite + ether.12 h in ice,12 h at RT.
Could be the IP extract/IP nitrite method better with ether?

Method of Thiele: 5 g Hydrazine hydrate + 37,5ml 4N solution of Natrium methylate + 12,5ml ethlylnitrite + 50ml ether
Method of Opelkin: stechiometric mix of NaOH + Hydraz.hydrate + ethylnitrite + ether
--
Method of Tanatar /Ber.32,S .1409/-hydrazin hydrate + NCl3(benzene solution)= HN3 + HCL
((my idea: Hydrazine sulf.+ aq.NaOH + NH4Cl --electrolysis==NaN3+NaCl))
---
Method of Curtius-hydrazine hydrate + HNO2== HN3+2H2O
Curtius- Kraus - hydrazine sulfate +KNO2 + H2SO4 all diluted and cooled in ice,,after foaming distillation.
((my idea: mix of Curtius/Kraus in adding funel on the two neck bottle dropped into boiling watter,the second neck has an usually cooler and distilled into bottle with NaOH solution.))
Method of Sobanejeff and Djengin(1899)-hydrazine sulphate 1,5g + 4 ml of HNO3/1,3/ bubbled through AgNO3.

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Theoretic - 11-1-2017 at 13:51

Method of Tanatar /Ber.32,S .1409/-hydrazin hydrate + NCl3(benzene solution)= HN3 + HCL
((my idea: Hydrazine sulf.+ aq.NaOH + NH4Cl --electrolysis==NaN3+NaCl))
[...]
Method of Sobanejeff and Djengin(1899)-hydrazine sulphate 1,5g + 4 ml of HNO3/1,3/ bubbled through AgNO3.

The first method is very interesting due to using a -III oxidation state nitrogen species, as the oxidizer. It is similar in principle to the Raschig hydrazine synthesis, where ammonia/amide nucleophilically attacks chloramine (here hydrazine attacks NCl₃), and resembles it more than the Curtius reaction!
However the electrolysis won't work, since chloramine (which you will get before trichloramine) quickly reacts with hydrazine and destroys it. This is the biggest issue in the Raschig process where chloramine concentration needs to be as low as possible.
The second one is cryptic. How does nitric acid create HN₃? If it's reduced by hydrazine to nitrous acid first, that's wasteful of hydrazine. The role of the silver nitrate is mysterious, and even more so what is being "bubbled" through it. There are no gases there.

Thraxx - 12-1-2017 at 00:32

To the NCl 3 method-
Hentschel (,Ber.1897,30,1434,1792) wrote,that NH4Cl react with sodium hypochlorite to form NCl3.
If the Tanatar wrote,that the NCl3 form with hydrazine the HN3,and if we do the hydrazine from NaClO,then it seems me be possible into reacted mix of Urea/NaOH/inhibitor/NaClO give the mix of NaClO + NH4Cl and expect ,that the NaN3 will be formed.(?)

To the methods of Thiele and Stolle-(isnt it the same publicated in the same time ?)
1866-Griess -Ann 137,39- Phenylazide from Benzenediazonium perbromide +NH4OH .
1878-Fischer- -Phenylazide from Phenylnitroso hydrazine + KOH
1890-Curtius -Benzoylazide +NaOH+Na ethylate
1907-Dennis and Isham -Azoimide
1908-Thiele-Ber.41,2681(1908)-ethylnitrite used
1908-Stolle-Ber.41,2811(1908)-amylnitrite used

To the method of Curtius-why react the hydrazine with HNO2 to azoimide,if it could react to its salt-N2H4.HNO2,colorless explosive crystals from alc. or ether.Moreover HN3 + HNO2==N +N2O + H2O.Therefore if there some azoimid toke place,then it should be destroyed.

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[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Theoretic - 12-1-2017 at 07:24

Chloramine reacts with hydrazine and destroys it. Did you even read my post.
"1866-Griess -Ann 137,39- Phenylazide from Benzenediazonium perbromide +NH4OH" - interesting variation. The N2 fragment has a nitrogen in a positive oxidation state this time. And the N1 fragment gets halogenated as before, but after reacting with the N2 fragment.

Thraxx - 12-1-2017 at 08:09

I would like to ask you,what could be the substance on the picture below.
This is product of my twelve experiments with IP alcohol extract of hydrazine sulphate + NaOH and adition of IP nitrite + NaOH.
Ever was it the same problem-there precipitate yellow-brown amorph watter solubile substance and after filtration and dilution in watter and precipitation with ethanol was this liquid outgoing .It is wattersoluble and non soluble in ethanol and aceton.
I dont know what it is or what it could be.Please help me ,this something is myChristmas.

PHILOU Zrealone - 12-1-2017 at 08:40

I would like to ask you,what could be the substance on the picture below.
This is product of my twelve experiments with IP alcohol extract of hydrazine sulphate + NaOH and adition of IP nitrite + NaOH.
Ever was it the same problem-there precipitate yellow-brown amorph watter solubile substance and after filtration and dilution in watter and precipitation with ethanol was this liquid outgoing .It is wattersoluble and non soluble in ethanol and aceton.
I dont know what it is or what it could be.Please help me ,this something is myChristmas.

It is stange you get a yellow colour and a brown-orange phase splitting.
To me you must have an impurity somewhere into your proces.

I have played with chemically pure N2H4.H2O and NaNO2 both mixed into water solution doesn't display any yellow color...when phenol-phtalein is added to both pink color is present but disappear when both solution are mixed (no bubbling) so maybe NaN3 formed?
I have played with N2H4.H2SO4 and NaOH and no yellow color.
I have played with N2H4.H2O and Cu(NO3)2, Co(NO3)2, Ni(NO3)2 and finally AgNO3...no yellow color...but beautiful colored complex precipitate (explosives) or decomposition into bubbles.

The phase splitting must come from NaHSO4 or Na2SO4 and maybe NaOH --> soluble into water but not that much into organic solvents.

The brown color maybe from some iron ... but then one of your ingredients must already be yellow or colored (normally all must be colorless, white, transparent); or maybe from oxydation of the isopropyl alcohol into aceton and crotonisation reaction with NaOH (brown tars)...but should be soluble into organic solvents more than into water...

Are you sure you are not trying to fool us with a picture of TNT trial from toluen and medium concentrated HNO3?Doesn't it smell bitter almonds? Really looks like nitrotoluen and dinitrotoluen oils...

[Edited on 12-1-2017 by PHILOU Zrealone]

Thraxx - 12-1-2017 at 14:05

"Are you sure you are not trying to fool us with a picture of TNT trial from toluen and medium concentrated HNO3?Doesn't it smell bitter almonds? Really looks like nitrotoluen and dinitrotoluen oils..."

I am sure,that it is not TNT and I am sure,that it is really problem for me,because I dont understand ,what this compound is or what it could be.May it be some nitrite?

The reaction mix is colorless first ten hours,after turn it more and more yellow.

I will repeat the reaction and I will make pictures of it.

[Edited on 15-10-2016 by Thraxx]

Theoretic - 12-1-2017 at 15:35

Philou: could this be oxidation of isopropyl nitrite, rather than isopropanol? Hydroxide E2 eliminates nitrite from IP nitrite, then the product is acetone, which condenses as you said.
Thraxx how much did you heat the reaction? Heating and lots of NaOH may make this happen.

Thraxx - 12-1-2017 at 22:08

Philou: could this be oxidation of isopropyl nitrite, rather than isopropanol? Hydroxide E2 eliminates nitrite from IP nitrite, then the product is acetone, which condenses as you said.
Thraxx how much did you heat the reaction? Heating and lots of NaOH may make this happen.

It was 12 reactions,only 2 was heated, 10 was cooled between -5 and 0 C .The heated was with liquid product,the cooled was with amorph product,which turned into liquid during precipitation with ethanol.
This product is in acetone insoluble.
After I heated the product with conc.NaOH,because I though,that it is some kind of organic azid,but it does no reaction.
I tryied to react it with AgNO3 and there precipitate something,but it wasnt energetic .

PHILOU Zrealone - 13-1-2017 at 06:05

@Theoretic,
If OH(-) eliminates nitrite from isopropyl nitrite it will be as NO2(-) and "isopropyl hydroxyde" what is the same as 2-hydroxy-propan, as 2-propanol or as isopropanol...the reverse of the ester formation --> hydrolysis.
So
Alk-O-N=O + OH(-) --> Alk-OH + ONO(-)
(CH3)2CH-O-N=O + NaOH -aq-> (CH3)2CH-OH + NaNO2
No oxydoredox involved and so no variation of oxydation state thus no aceton/propanon from isopropanol that way.

@Thraxx,
You didn't gave an answer about the purity of your reactants.
Commercial aceton, NaOH or isopropanol may get some crap % of impurities. NaNO2 may aswel depending on its proces.

Test with AgNO3 will give a precipitate with many compounds into your reaction media:
-nitrite; AgNO2 is a white-precipitate that darkens under light.
-hydroxyde; AgOH is turning instantaneously into black-brown Ag2O.
-hydrazine; generally decomposed as N2 and silver mirror or black colloidal Ag
-sulfate; yield unsoluble Ag2SO4
-azide; yielding AgN3 precipitate
-other unknown crap...many Ag(+) salts are unsoluble or weakly soluble precipitates

[Edited on 13-1-2017 by PHILOU Zrealone]

Thraxx - 13-1-2017 at 07:06

@Thraxx,
"You didn't gave an answer about the purity of your reactants.
Commercial aceton, NaOH or isopropanol may get some crap % of impurities. NaNO2 may aswel depending on its proces."

Purity... NaNO2- P.a.
IP alcohol- pure
KOH-pure
NaOH-technical grade
IP nitrite-(made with HCl technical grade) new before each reaction,but only 2x washed through shaking with 0,5l watter.
Rations and possible mistakes :
1.extraction (Hydr.sulf. 1 mol + 1mol hydroxid +IPA (50 ml for each 30g of HS )IPA for 20 min to 5 h,either cooled in ice or heated in bath+ 1 mol hydroxid for 30 min.)
2. extraction with other 50 ml IPA/30g HS
In more cases,if was it cooled in ice was the separation bed and I must use vac.filtration.
3. To the extract was added solution of 1 mol hydroxide in bigger amount of IP alcohol or in watter and after shaking was added 1 mol of IPnitrite.

May be ,that in extract was not enaught of hydrazine hydrate and the amount of IPnitrite and hydroxide was too big.
May be,that the solution of hydroxide in IP alcohol was poridge with small pieces of hydroxid,which came into touch with IP nitrite and caused its destruction.
In these days I will repeat the reaction and its pictures with description I will give here.

---once more-on the picture of the strange liquid there is something about 50 ml. It stay all night in freeze below the window and now is there only about 30 ml.It seems me like alcohol in thermometer.Could the liquid be something like eutectic solution of NaNO2 in IP alcohol?

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

Semicarbazide ?

Thraxx - 14-1-2017 at 07:45

I decided me to do semikarbazide and from it make the sodium azide.This method I found elsewhere here in this forum.

Semikarbazid from monochlorurea:
1). solution of 9 g Urea in 125 ml watter -
2) 150 ml bleach slowly with little strom pour to the solution (1)
-
3) solution of 2g ZnCl2 diluted in 50 ml of 20% NH4OH -
4) boil it to lost of smell
5) give there second 50ml 20% NH4OH
6) boil it to dryiness-I did it on flat steel beaker behind window and there was a terrible much of foam-pic 4 and 5
7)after evaporation there was not much of product of Semicarbazide?.
8) To this product I poured a lot of 30% HCl and there precipitated white crystals,which I though was Semicarbazide Chlorid,which I filtered.. There was about 5 g of it.
9) For to make azide of this stuff ,I diluted it in 5 ml watter and gave there 5g NaNO2(solution).In this moment should turn the semikarbazide chlorid into Carbamoylazide,which is very good solubile in watter and alcohol.But there appear white precipitate.But I wanted azid and therefore I added there 5g of NaOH(solution) an boiled it.The precipitat stay there.But I wanted azide and therefore I gave there some amount of watter,and after amount of alcohol for precipitation of the wanted azide.Solution ,brown collored really begann precipitate something dark.

conclusion- I think,that the product is or better was hydrazinodicarbonic acid diazide.

[/file]

[Edited on 15-10-2016 by Thraxx]

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Theoretic - 16-1-2017 at 14:06

If OH(-) eliminates nitrite from isopropyl nitrite it will be as NO2(-) and "isopropyl hydroxyde"

It won't! That's substitution you're talking about; it's not elimination. That's why I specifically said "Hydroxide E2 eliminates nitrite from IP nitrite". E2 elimination.
OH- won't displace nitrite to form isopropanol; OH- isn't a very good nucleophile and NO₂ isn't a very good leaving group, with the C-N sigma* antibonding orbital at a too-high energy to react with hydroxide.
If hydroxide ever 'displaces' the nitrite, it happens by addition to the N center, then elimination of isopropoxide anion.

[Edited on 16-1-2017 by Theoretic]

Thraxx - 17-1-2017 at 02:37

About the IP extract + IP nitrit method.
Schema of reaction:
HS Extract (3 times) + NaOH + IP nitrite == NaN3 + Na2SO4+IPA
1/8 mol=16g + 5g + 13ml == 7,5g

Extracted was 5 h at RT ,reaction was 24 h at -5C in freezer.Precipitated was with 3 vol. of ethanol(tech.)+aceton 1:1

Pictures: 1,2,3= extraction chemicals and extraction beaker
4=extract + NaOH solution in 40 ml IPalc.
5= extract with NaOH sol + IPnitrite=reaction mixture
6= the reaction mixture after 12 h.
7= reaction mixture after 24h.
8,9,10,11=filtration and amorph product
12=giving the product in the beaker before diluting
13 =product diluted in watter,very solubile
14=precipitation with alc./aceton mix
15=precipitation after 12 h. in freezer at -5C=ZERO
Conclusion: This reaction I did 13 x.Only one of these was with yield,all other reactions produced either dark liquid or ,like this -nothing.Does somebody knew what is wrong or what to do for to have some yield?

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

PHILOU Zrealone - 18-1-2017 at 00:29

If OH(-) eliminates nitrite from isopropyl nitrite it will be as NO2(-) and "isopropyl hydroxyde"

Oh yes I understand now. I simply reused your "eliminates" without noticing the E2.
Yes I was speaking of substitution.
The case of nitrite esters is a hard one because into water they are extremely unstable...while they are very easily made from dilluted HONO (what is in strong opposition with most other esters that require concentrated acid and water scavenging to schift equilibrium to the right side of the reaction).
In fact the nitrous ester suffer from very easy retroconversion into the alcohol and nitrous acid...in fact as fast as it was done.
HO-N=O + Alk-OH <===> Alk-O-N=O + HO-H
The reaction is almost instantaneous and may go via several pathways:
-nitrosonium exchange with a proton form water (most probable)
-hydroxyl exchange with a nitrite anion (probably too slow)
-protonation of the alcohol, elimination of water to make carbocation and attack of the nitrite to leave a proton (probably too slow)

So nitrite esters are sensitive to base, to acid like most esters but also to neutral water; leave a nitrite ester for a few seconds into water and it has already reached decomposition/recomposition equilibrium.
This is the reason organic chemistry likes this reactant so much.
Easily done, easily collected and very reactive (fast reacting).

Thraxx - 18-1-2017 at 13:00

Well,but what could be the strange liquid?Hydrazine is reducing. agent.Alcohol is not possible to be reducted,but what the HNO2?Could it be reduced into HNO azanone ? And is the azanone able to react with hydrazine or alcohol?
---
If the problem is in the lability of alcohol-nitrite,then it should be added either in drops,or it should be diluted.In the old methods they have a big part of diethylether.May be this is the reason-ether is a solvent for alcohol-nitrite.
From other point of view,in Urbanski,part III.under Baryum azid is described such method,where is ading of ethylnitrite during more hours and is freezed under -15C.
May be,that the IP extract/IPnitrite method need ether. Or an dropper.

[Edited on 15-10-2016 by Thraxx]

[Edited on 15-10-2016 by Thraxx]

PHILOU Zrealone - 19-1-2017 at 09:07