Improvised Sodium Azide

[Microtek]

For some time now, I have been searching for a substitute for HMTD as I have been growing dissatisfied with this substance.
I had set my sights on either DDNP or heavy metal azides, as performance had to be at least equal to HMTD. After a lot of failed attempts, I finally got some usable results:
1.3 grams of hydrazine sulfate ( made from NH4OH + NaOCl ) in demin water was reacted with 3.3 grams of Pb(NO3)2 also in water.
The PbSO4 was filtered off and the water evaporated to obtain hydrazine nitrate. This HN was placed in a distilling flask and just enough water was added to dissolve it ( a few drops ).
0.4 grams of NaOH in about 1 mL water was added to form hydrazine hydrate soln.
5 mL ethanol with as much NaOH as could be dissolved therein was added to the flask, and it was placed on the hotplate with a long glas tube for refluxing.
0.8 mL isopropyl nitrite was added gradually while the contents refluxed ( should have been 1.3 mL according to FEMFEP but I ran out ) and the flask was left on the plate for 15 min after addition was complete. Insignificant amounts of precipitate was observed on cooling, so the flask was fitted with a rubber stopper and left at room temp for 48 hours.
A very small amount of crystals had formed on the bottom and these were filtered off and dried. The filtrate was poured into an evaporating dish and left outside in the sun.
The first batch of crystals were tested by dissolving in demin water and adding Pb(NO3)2 soln. White precipitate formed but it was found to be non-explosive ( I assume Pb(OH)2 ).
When all liquid had evaporated from the evaporating dish, an amount of white crystals remained. When these crystals were dissolved in water, the soln was found to be strongly alkaline ( much of the crystalline mass was NaOH ) and in an attempt to avoid precipitating the hydroxide of lead or silver, I added dilute HNO3 slowly and with some effervescence until the soln was slightly acidic.
When AgNO3 soln was added, white precipitate formed and was collected by filtration. The product was found to detonate violently when exposed to flame.

<small>[ May 15, 2002, 04:51 AM: Message edited by: Microtek ]</small>

[Pu239 Stuchtiger]

If you can prepare Pb(NO2)2, you can prepare Pb(N3)2 much more easily.

2N2H4 + Pb(NO2)2 --> Pb(N3)2 + 4H2O

[James]

Microtek, you seem to have an unbalanced reaction there. Where is the sulfur coming from?

[Microtek]

Pu: Yes and it should be possible with AgNO2 as well, and the preparation of AgNO2 is as easy as AgCl, but I can't seem to get the azide to form...

James: The hydrazine hydrochloride is made from the NH4OH reacting with NaOCl but this is precipitated with sulfuric acid as the sulfate is not very soluble in cold water. It's a standard synthesis so I didn't think it was neccessary to explain it.

[Mr Cool]

You mean isopropyl nitrite, not alcohol, right?

<small>[ May 14, 2002, 04:53 PM: Message edited by: Mr Cool ]</small>

[Microtek]

Yes, I do. The error has been edited. BTW, I'm a bit surprised that so few have responded as azides are really excellent initiators. Perhaps the hazards of preparing hydrazine are the reason, but if this is the case I think it is possible to order it on the net as it is not very dangerous ( the lethal dose is something like 600 mg per kilogram bodyweight, meaning that I would have to eat about 50 grams to kill myself; NaCl is lethal in those amounts ).

[megalomania]

I do believe I have the synthesis for most of those precursors on my website if anybody would like to take a gander (I need to fix my search on there).

Ahh yes, I have <a href="http://roguesci.org/megalomania/explo/IPN.html" target="_blank">isopropyl nitrate</a> and <a href="http://roguesci.org/megalomania/synth/synthesis2.html#hydrazine" target="_blank">hydrazine</a>. My hydrazine procedure is modified from the original hydrazine sulfate procedure which nbk2000 has posted here, or the original can be found at <a href="http://www.orgsyn.org" target="_blank">www.orgsyn.org</a>

<small>[ May 15, 2002, 12:22 PM: Message edited by: megalomania ]</small>

[Polverone]

I thought that the azide manufacture used isopropyl nitrIte, not nitrAte. That's a pretty nice hydrazine preparation, though I confess that I'm not going to be able to distill under an inert atmosphere anytime soon.

[Microtek]

Yes it is nitrIte, and note that if you are going to use the hydrazine to make azide, you don't need to distill. I reccomend that anyone inerested had a look at the ftp. There is a pdf called chem.pdf which contains 20 pages from an old chemistry book. In these pages are descriptions of both hydrazine production on a lab scale and sodium azide synthesis from a number of different routes. Definitely of worthwile read.

PS: The isopropyl nitrite is incredibly volatile; it boils at about 37 C and at room temp it will shoot the stopper out of the bottle after standing just a few minutes. It can be kept for days at -20 C ( in the freezer ) - when I did the addition I sucked it up into a syringe and put it back in the freezer between adding the portions.
Note also that it's a vasodilator like EGDN, so avoid breathing the fumes. The danger of skin contact is probably not that great; I spilled some on my hand ( stupidly wearing gas mask but no gloves ) but before I could get to the sink to wash it off, it had all evaporated. I washed it anyway and never felt a hint of headache.

<small>[ May 16, 2002, 09:10 AM: Message edited by: Microtek ]</small>

[da man]

Sorry to bring up an old topic, but i have some questions about making azides from hydrazine.
Microtek, when you are making the hydrazine sulfate, what concentration sodium hypochlorite solution did you use, is household bleach adequate, or would the small amount of sodium hydroxide interfere? Or did you make the sodium hypochlorite yourself from chlorine and hydroxide? And what were the ratios for ammonia, sodium hypochlorite and calcium hydroxide used?
When i react the hydrazine sulfate with KOH to make hydrazine hydrate, do i need to distill or reflux, as it says in the book on the ftp that you mentioned, and is the distilling dangerous?
Also for the reaction N2H4 + Pb(NO2)2 = Pb(N3)2 + 4H2O that Pu239 gave, can i use dilute hydrazine hydrate, or does it require anhydrous hydrazine?
So basically, first i make hydrazine Hydrochloride by reacting NaOCl with ammonia, and CaOH. I then add sulphuric acid to precipitate hydrazine sulfate. I react this with lead nitrate, precipitating lead sulfate, and leaving hydrazine nitrate in solution. I react the hydrazine nitrate solution with KOH to make hydrazine hydrate, which i then react with Pb(NO2)2 to make PB(N3)2.
BTW can PB(NO2)2 be made by reacting lead nitrate and potassium nitrite?
I'm sory about all the questions, but im really interested in making azides. Thankyou for all the help!

<small>[ June 18, 2002, 08:11 PM: Message edited by: da man ]</small>

[Microtek]

I used a no-name brand of bleach which worked fine.
I don't think you need to reflux the hydrazine nitrate with KOH to make that hydrate and you certainly shouldn't distill ( that's when it starts to get really dangerous ).
The reaction between hydrazine and nitrite takes a while. I refluxed it, and then let it sit for a few days.
( I had written a great deal more but it was deleted when I hit the back button so this is a summary - the most helpful advise that I have is to dilute the H2SO4 to about 50% before adding it dropwise to the hydrazine hydrochloride soln, otherwise the liquid will boil and this will cause the gelatine to foam which will interfere with collecting the hydrazine sulfate )

Feel free to ask further if anything is still unclear.

[da man]

Thanks microtek!
What do you mean, by make the gelatine foam, it says also in that pdf on the ftp that when you add the sulphuric acid a gelatinous mass precipitates which isn't the hydrazine sulfate, what is this?
And in another post about hydrazine it was said that you need glue or EDTA to make hydrazine sulfate, did you use this?
Also what were the ratios of the different chemicals you used?
And is it really necessary to add the lime water?
And in the pdf on the ftp he turned the hydrazine sulfate straight to hydrazine hydrate, without making hydrazine nitrate, why did you turn it into hydrazine nitrate, before reacting it with KOH?
Lastly what were the yeilds like?
Thanks for all your help, have you gone on to succesfully making lead or silver azide from this method, or was it just an experiment?

[Microtek]

For the reaction to work, you need to add some sort of colloidon to the mix. This can be gelatine, starch or glue ( or possibly EDTA ) - according to Merck, gelatine is by far the best.
This is a page where the synthesis of hydrazine sulfate is explained in detail. I used these ratios except where I needed to adjust for differences between the concentrations of my chems and theirs.

<a href="http://www.bookrags.com/books/rgsyn/PART11.htm" target="_blank">http://www.bookrags.com/books/rgsyn/PART11.htm</a>

The lime water is needed for the production of hypochlorite, but I suggest that you buy bleach instead of making your own ( you need a lot of chlorine gas and you might not get a very pure product ).
The reason I converted the H-sulfate to the H-nitrate was two-fold:
Firstly, I didn't want any sulfate ions in the sodium azide as that would react with the lead ions when I tried to make lead azide.
Secondly, it takes about 500 times as much water to dissolve hydrazine sulfate as hydrazine nitrate, so you can make a more concentrated hydrazine hydrate soln.
The yields where OK but not great...
I think I got about 6 grams of HS from 50 mL of 15 % hypochlorite, a little less when I used bleach ( 5% NaOCl ).
I don't know what the yield of sodium azide was. The product that I ended up with had a lot of NaOH in it, but I don't know how much. The NaOH doesn't matter for silver azide production, you can just neutralize the soln with a little HNO3; not too much though or you will make HN3 from the NaN3. This hydrazoic acid is volatile and very poisonous ( and it wastes your sodium azide ).
I found that silver azide was easy to make by mixing silver nitrate soln with a neutralized soln of sodium azide. The AgN3 was precipitated immediately. I didn't succeed in making lead azide, but then I haven't tried that much as I don't want to waste my precious NaN3.
Oh, about the gelatine foam... If you add H2SO4 to the boiled down solution of hydrazine hydrochloride, gelatine and byproducts, the water will boil from the heat liberated when the sulfuric acid rects with water. This boiling water will blow bubbles in the viscous liquid and because of the gelatine, these bubbles will be very persistent.
I hope that answers your questions.

[Polverone]

I know that it's advisable to use a large NH4OH excess with the hypochlorite. Did you use household ammonia solution, or concentrated stuff? I've wondered about trying to use calcium or lithium hypochlorite (since you can get them at much higher concentration than bleach) with ammonia gas bubbled in for high concentration...

On the other hand, I am not eager to expose myself to hydrazine. But based on your success I just might try to join "Club Azide."

Do heavy metals in general make explosive azides? If so, I'm gonna have to try... uranium azide! The ultimate exotic primary, for entertainment purposes only.

[mongo blongo]

Uranium Azide! Well I don't know about that but that could be mad! I know that there are a lot of metallic Azides but the organic Azides is where the fun begins. Have a look into Azido binders, very interesting. <img border="0" title="" alt="[Wink]" src="wink.gif" />

[Pu239 Stuchtiger]

Why not Pu(N3)4? <img border="0" title="" alt="[Wink]" src="wink.gif" />