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garage chemist
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Sodium nitrite has appreciable solubility in ethanol. I don't think it would precipitate.
And the washing of the NaN3 with ethanol would remove any nitrite.
I'll do the freebasing again when I have my clean ethanol.
So I should mix all of the NaOH with the HS, and then take up the formed hydrazine hydrate with ethanol?
Or could I add ethanol to the HS and then add the NaOH in two portions, like I've been doing, just with good cooling?
Microtek adds the alcohol from the beginning. I like that method because everything is covered with liquid and the ethanol fumes protect the hydrazine
from oxygen to some degree.
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Rosco Bodine
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I have freebased 2 moles of HS at one time in a 1 liter Erlenmeyer , using the
alternating additions method I have described , where first 1 mole HS is converted to a hot liquid solution of the dihydrazine sulfate by portionwise
additions of about a quarter
of the NaOH used for the freebasing , the second mole of HS added to the hot liquid
in alternating portions with the second quarter of the NaOH , keeping the mixture very hot and stirrable to the completion of the additions . The
second half of the NaOH is then added in portions , likewise maintaining the heat of reaction and even adding some low heating from the stirplate to
keep the mixture hot during the final quarter of the freebasing . Stirring is continued and as the cooling mixture thickens and has cooled just
sufficiently to prevent flash boiling of the alcohol , the first and largest portion of alcohol is added in a lump to the stirred slurry , stirred for
ten minutes and decanted while still very warm . At least two fresh portions of alcohol are added , each being stirred up and decanted , the extracts
being combined . The combined extracts are chilled and then the added portion
of NaOH for the formation of the NaN3 is
added as a solid in portions , being dissolved in the combined extracts .
Using methanol this has proven to be an efficient method . However it may be that
a different sequence is better or even essential for avoiding problems using another alcohol . This is known to be so for isopropanol , which is the
complication
found to be remedied by microteks method of wetting the HS first with the alcohol . Personally , I don't believe the freebasing proceeds to
completion nearly so completely nor rapidly in the nonaqueous condition .
Perhaps it is only a matter of time and the freebasing does go to completion even in alcohol . I have not done any quantitative result comparisons so
I can't be certain of which is more efficient . It is just my guess really that the freebasing is better accomplished in the aqueous phase due
to the ready solubility of the dihydrazine sulfate intermediate
in the water present , as compared with a poor solubility in alcohol . This would be mitigated by limiting the quantity of alcohol used , so that the
" moist alcohol "
provides sufficient water content for the freebasing to proceed at a limited rate , while having too much alcohol initially would quench the
freebasing reaction . The disadvantages are perhaps insignificant simply by refining the method , knowing that a particular amount of a particular
alcohol establishes a condition favorable to the freebasing , while just any quantity
randomly chosen may give poor results due to the fact that the water content is what enables the reaction to proceed .
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Quince
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| Quote: | Originally posted by rogue chemist
Your welcome a_bab.
Sodium azide scans have now been uploaded. Same spot as before |
I can't find this anywhere. Looking in the sciencemadness library, the keyword azide is not anywhere on the page.
\"One of the surest signs of Conrad\'s genius is that women dislike his books.\" --George Orwell
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The_Davster
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The scans are on the ftp under 'rogue chemist', not in the library.
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SAM4CH
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Hydrazinium Azide
how can I prepare Hydrazinium Azide from hydrazine sulfate or hydrazine hydrate and inorganic azid salt "soium azide"?
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Axt
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Your after US patent #3155456 "Process for Preparing Hydrazinium Azide" Attached, Reflux hydrazine sulphate and sodium azide in n-butanol.
[Edited on 15-4-2007 by Axt]
Attachment: hydrazinium azide.pdf (328kB)
This file has been downloaded 1666 times
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anne_atdf
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hy
i search what is the reaction with oxybis(benzenzsulfonyl azide) (N3-SO2-C6H4)2-O ?? do you know how it can react with H2O, O2 or with thermal
decomposition??and what is the condition? i you know tell me please, i'm desperate!!
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nitro-genes
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Just out of curiosity, but I've seen several MSD sheets for silver(I)diamine solutions (tollens reagent) mention formation of silver azide on storage.
First I thought it was a mistake, and that they meant silver nitride complexes that are generally formed from ammonia and silver(I), though these
nitride complexes are dark coloured, usually black compounds while one of the MSDS clearly mentions formation of highly explosive colourless
crystals...
Any idea of this is true? I can't really envision how azides would be formed this way. 
I would be cool though, just heating a silver(I)nitrate solution with excess 30% ammonia, so that the formed silverazide would stay in solution, then
distilling off some of the ammonia by heating until clouding can be observed, followed by addition of some acetic acid to provide crystal nuclei
(US3943235) to yield one of the most efficient freeflowing primaries in a one pot reaction. Even if the yield woud be terrible (very probable), the
silver nitrate could easily be reclaimed from the solution...
Nehhh, just too good to be true...
[Edited on by nitro-genes]
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The_Davster
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I keep hearing unsubstantiated claims as well. All regarding hydrolysis of nitrides to azides, however given that there are so many misconceptions,
even among those in academia, regarding silver-nitrogen explosives, it is not a surprise.
I had one professor at one point mention that magnesium nitride hydrolyses in water to N3- (which he did not know the name for, oddly), and have heard
all manner of claims from professors regarding the old silver ammonia precipitates all sorts of things including silver azide, fulminate,
hydrazide(?). I suppose those without direct interest in the chemistry here take what they hear from somewhere incorrectly, and pass it on.
I believe it is too good to be true, but would enjoy being wrong.
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nitro-genes
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I doubt the formation of the azide as well, even the colour of the product may be deceptive as I've read that the black colour of the silver
nitride/imide complex could also be caused by the presence of elementary silver as well as traces of silver oxide, which would be absent when slowly
left to crystallize.
The silverazide supposedly only forms on prolonged storage unlike silver nitride, so one of the things that could explain the formation of azides is
oxydation of the silver imide/amide with the excess ammonia and oxygen from the air.
In any case is it likely that the product would be contaminated with substantial amounts of silver nitride rendering it too dangerous to be of any
practical use.
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crazyboy
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Does anyone have a synthesis for silver azide by using an aqueous silver nitrate and aqueous sodium azide? I would like as specific instructions as
possible not just theoretical formulas. ie temperatures, heating, cooling and mixing if necessary. Thanks in advance.
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The_Davster
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It is a simple metathesis...mix solutions, stir, filter, wash.
If such simple chemistry is unknown to you, it would be inadvisable to start with preparing a compound as sensitive as silver azide.
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crazyboy
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This is not the first energetic compound I have prepared however I like to go into things with full awareness of what to do or what to expect. Not
being aware of these things is how accidents happen. and as you mentioned an accident with a compound as sensitive as silver azide would could be the
last one you ever make.
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Sickman
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The Manufacture of Silver Azide R.D. 1336
@The_Davster,
You know with all the seemingly millions of "recipes" for the manufacture of organic peroxides floating around on the internet I feel the world is
just a little safer every time a good azide synthesis is posted or even just a link to a good azide synthesis.
Honestly I'd rather see the supposed newbie, Crazyboy, try his hand at silver azide than to loose a hand with the organic peroxides.
So here you go Crazyboy:
The following link is to a military report on the synthesis of silver azide for use in service detonators by the U.S. Military.
It is dubbed The Manufacture of Silver Azide R.D. 1336. If you right click on the link and select "save target as" you can download and view the pdf file which
is about 3.55 Mb. The report is 24 pages in length and describes a three pound batch size which of course you can scale way down to even milligram
batches if you want to and should. 20 degrees Celsius is the desired operating temperature during the entire synthesis. Yields are very high according
to the report and the resulting silver azide is of a satisfactory density and stability, and initiatory abilities are higher than that of service lead
azide, which today is the current king of primary explosives, in my opinion!
A word to the wise: Only make silver azide in manageable amounts. For example half of a gram or less at a time. Wear safety glasses all the time and
thick cowhide gloves. Don't put any material of substance, such as glass or metal between you and the primary explosive, unless a strong shield such
as a thick peice of plexyglass is used. If you are to load a metallic blasting cap with an explosive, drill a cap sized hole in a thick block of wood,
and then press the cap in the block. That way if an accident should occur the block of wood gets hurt and not you!
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woelen
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I would say, don't make half a gram, but only make at most 100 mg. You will be surprised how loud a bang such a small quantity can give. An explosion
of this quantity inside the house will give you pain on the ears. You then can work at test tube scale, with test tubes wrapped in a towel. If the
stuff explodes, then you won't hurt your hand, the towel will be damaged. Do wear safety glasses, even with 100 mg quantities.
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The_Davster
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From the book that started this thread.
(any errors I missed were from the OCR)
| Quote: |
Silver Azide, AgN3, is a white crystalline solid which is photosensitive and has the property of explosion. The technical product is often gray. The
azide is practically insoluble in water and organic solvents. Aqueous ammonia [ l ] or anhydrous hydrogen fluoride [196] dissolve it as a complex;
upon evaporation, the azide is recovered unchanged. Colorless needles more than 10 mm long are easily obtained from the ammonia solution [197]. In
nitric acid it dissolves with chemical destruction, evolving HN3 gas. On exposure to light, silver azide turns first violet and finally black, as
colloidal silver is formed and nitrogen evolves [175,176]. As photographic emulsion, the azide is found to be 200 times less photosensitive than
silver bromide, but more easily reducible by developers. The emulsions are not explosive [198]. A suspension of silver azide in boiling water
decomposes with a discoloration similar to that of the photodecomposition [176]. When heated dry, the azide turns violet at 1 50'C and melts at 25 1OC
to a blackish liquid. Starting at 253'C the melt evolves nitrogen gas at a rate which simulates boiling. The mass then shrinks to a brown solid and
finally, at the end of decomposing, appears white. Under the microscope the particles appear as silver metal (21. When heated rapidly, silver azide
explodes at 3W°C with high brisance, emitting a green light flash [1,2,176]. A partially (50%) decomposed, gray sample explodes with the same
brisance at 305'~ [176]. The degree of decomposition has evidently little influence on the explosive behavior. The same was found for mechanical
explosion; white and gray samples are equally highly sensitive to friction and impact
(1991. However, the particle size has a distinct influence on impact sensitivity; coarser samples are more sensitive [l92,200]. Long needles of silver
azide frequently explode when broken with a metal wire [197]. The AgN3/N3- half cell assumes a standard potential of +0.384 V at 21 "C; the solubility
of silver azide in water was electrochemically determined as 8.4 X g/liter at 18OC [201].
Of historic interest is a reaction in which the azide group was synthesized from hydrazine and nitrite in the presence of silver ions [19,98] (see p.
24). Most commonly, silver azide is prepared by mixing aqueous solutions of hydrazoic acid or sodium azide with silver nitrate. The product is
precipitated in fine crystalline form; larger crystallites are obtained from more dilute reagents [200]. One author recommended the use of an excess
of sliver nitrate; another believed this would enhance the photodecomposition of the product [202]. Of more significance is the recommendation to make
the azide in the dark, or at least under red light, [203.204] and to wash the product completely ion free.
To prepare 3-g batches, a solution of 3.42 g silver nitrate (slight excess) in 100 ml water is placed in a 500-rnl beaker and heated to 60-70'~. The
solution is stirred with a rubber-clad glass rod, and a solution of 1.3 g sodium azide in 100 ml water (60-70'~) is added within 3-4 min. The
precipitate is stirred until well coagulated and then transferred to a Buchner funnel. To avoid contact with the hard funnel material, both the bottom
and walls are covered with filter paper. The product is washed with water until nitrate free, thed h alcohol and ether, followed by drying at
70-90°C.
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One should be very carefull, as these compounds can explode under water, so glass stirring rods are a no-no. And as mentioned, use small ammounts.
The above synthesis I believe is tailored to a silver azide product more suited for practical use, wheras if you need only a few mg for demonstration
of the explosive effect, simple azide and silver solutions can be mixed without any special procedure. I have done such before without issues.
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microcosmicus
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Could you provide a bibliographic reference (i.e. title and author) for this
500 page tome on azides which you have been referring to as "the book"?
Reading through this thread, I have seen plenty of quotations, but none
of the information which would allow me to track down a copy at a
library near me.
[Edited on 14-2-2008 by microcosmicus]
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The_Davster
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Silly me, I cannot believe I never did.
Energetic Materials. Vol. 1. Physics and Chemistry of the Inorganic Azides. Edited by H. D. Fair and R. F. Walker
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Engager
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Hi all, i have some comments related to azides. First off all stay away from HN3, not even it is highly explosive, it is also very volatile and highly
toxic. It's fumes can detonate on contact with sharp surfaces and at slight pressure change. Boiling point of HN3 is just above 35C, and if you place
it in cold beaker it can condense on side walls forming hazardous concentrated HN3 drops. Never add acids to cold solution of azide!!!
Stay away from copper azide, i know guy who made it and it detonated in his hands while he suddenly broken small crystall, also it can expode
underwater if crystalls are big enough. Remember that Co and Ni azides are total suicide, they are extremely sensitive, in dry state whey detonate
even then trying to move it with soft brush.
Pb azide can also explode while precipitation from water solution because inner crystalline stresses, always pay attention to make only small
crystalline forms and stabilise them with binders such as dextrin.
Azides are very toxic, they disturb redox reactions in organism, destroy erythrocytes in bloodstream and oxidize hemoglobine to methemoglobine. Also
be aware that not harm and fatal concentations for HN3 are very close (same way as HCN), and not-fatal doses of HN3 can cause delayed effects.
Toxicological action of HN3 and HCN is the same, and toxicity is close to each other. Azides have same action as cyanides because of same toxicity
mechanism. Hydrazine is also highly toxic and is nerve system poison, destroys liver and affects high nerve system activity.
All inorganic azides except alkali metall ones are explosive, lithium azide is also explosive. Organic azides containing more then 25% mass azide
nitrogen are also highly explosive and should be handled with great care. Some organic azides are good primary explosives, the most famous one is
cianuric triazide. Nitrogen rich azides such as tetrazylazide or isocyanogentetrazide are terribly brisant and sensitive.
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chemoleo
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| Quote: | | Remember that Co and Ni azides are total suicide, they are extremely sensitive, in dry state whey detonate even then trying to move it with soft brush
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and
| Quote: | | All inorganic azides except alkali metall ones are explosive, lithium azide is also explosive. |
Could you please reference this.
For cyanuric triazide, look up COPAE, it can be prepared by reacting cyanuric chloride with NaN3.
Cyanuric chloride is in turn prepared by passing chlorine gas through HCN (in Et2O or CHCl3), forming extremely toxic cyanogen chloride ClCN in situ.
[Edited on 22-2-2008 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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quicksilver
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Does anyone have references for molecular weights in relation to energetic reactivity? Simply put, I see density playing a role with mercury and lead
and higher sensitivity with copper and silver but yet there seems exceptions depending on the energetic material, so I want to learn more. I have yet
to find anything relevant....
Copper azide is unbelievably sensitive, silver much less so, the phenomenon continues with mercuric and lead azide. Why such a differentiation in
sensitivity????
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Engager
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H.D. Fair , R.F. Walker - Physics and chemistry of inorganic azides pages 47,48:
Russian reference L.I. Bagal - Chemistry and technology of primary explosives, page 261:
Translation: Anhydrous cobalt azide (crystalises with one molecule of water) is brownish-red crystalls with melting point 148C (detonation
decomposition). Hygroscopic, extremely sensitive to friction (detonates even from friction between lists of paper), extremely sensitive to shock. Thin
layer of cobalt azide ignited by hot wire gives detonation velocity 3400 m/sec. Detonation velocity did not changed after neutron bombardment.
Russian 5 volume chemical encyclopedia, Volume 1, page 48:
Translation: Metal azides are crystaline substances (see table above). They are unstable: in many cases friction, impact, heating and light cause
explosive decomposition, sometimes explosion can occur than handling wet azide or even in solution. Only azides of alkali metals (except Li) are
capable to decompose without explosion.
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quicksilver
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Thank you. I wish there was an English translation of L.I. Bagal. I have seen a lot of Russian material that I would love to read. You're lucky to
have those language skills!
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math
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which book was it davster?
chemistry of inorganic azides maybe?
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The_Davster
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| Quote: | Originally posted by The_Davster
Energetic Materials. Vol. 1. Physics and Chemistry of the Inorganic Azides. Edited by H. D. Fair and R. F. Walker |
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