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The_Davster
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cool.gif posted on 9-5-2004 at 13:13
Azides


A few days ago I went to the University library and got an entire 500 page book on inorganic azides. The book gives synthesis of all inorganic azides(metal and nommetal) and how to crystallize them, electronic structure, lattice dynamics, decomposition, etc..etc. Unfortunalty I do not have a scanner, otherwise I would upload it to the FTP. So if anyone wants info on any inorganic azide, I'll gladly retype the info that is wanted.
Something that I learned from this book that I did not know before was that there are 3 types of lead azide, with varying degrees of stability.:P
Keep in mind I only have 2 weeks with this book, but if there is enough demand for info I will renew it.
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[*] posted on 9-5-2004 at 15:56


Would there be such a compound as antimony triazide? If so, it would astound me... And what about ammonium azide?
I think it would decompose th Hydrogen and nitrogen rather violently.
NH4N3-->2N2+2H2




F. de Lalande and M. Prud'homme showed that a mixture of boric oxide and sodium chloride is decomposed in a stream of dry air or oxygen at a red heat with the evolution of chlorine.
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[*] posted on 9-5-2004 at 16:29
Azides of Antimony


"metallic Sb dissolves very slowly in hydrazoic acid, and owing to hydrolysis, no azide containing products can be isolated. Some organoantimony azides are known, such as the liquid (C6H5)2SbN3, which resembles the respective P and S compounds. A low azidized compound of Sb(V), the yellow crystalline SbCl4N3 explodes on mechanical and thermal shock. Thermal decomposition starts at 107C and leads at 131C to melting sometimes with exploding. The compound is obtained by azidation of antimony pentachloride with chlorine azide or with trimethylsilyl azide. Equally explosive is the yellow anion[SbCl5(N3)]- which is obtained as the crystalline potassium salt from SbCl5 and potassium azide in liquid SO2. The complex dissolves in water with hydrolysis and in polar organic solvents."
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[*] posted on 9-5-2004 at 16:43


Does your book have any information on Aluminum tetraazidoborate Al[B(N3)4]3 ? All I have found on this compound is that it is a very shock sensitive explosive but it has always been somewhat intriguing to me.



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The_Davster
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[*] posted on 9-5-2004 at 17:20
Ammonium azide


"Ammonium Azide
This compound, of the interesting empirical formula N4H4 has the properties of a typical ammonium salt. At 20C, 100mL water dissolve 20.16g; 100mL methanol, 3.27g; and 100mL ethanol, 1.06g. It is easily recrystallized from hot methanol or precipitated with ether.
Like ammonium chloride, N4H4 dissociates thermally below the melting point according to NH4N3<--> HN3 + HN3 , but the tendency here is so pronounced that the vapours are completely dissociated at room temperature, and the substance volatilizes quickly when left uncovered.
The thermal dissociation of N4H4 is frequently mistaken for sublimation. It has been reported with a note of surprise, for example, that the salt explodes when heated in a sealed system, but not in open air. These explosions stem from a pressure build up of free HN3 in the vapour phase. Likewise, older reports on the temperatures of thermal decomposition, sublimation, and deflagration do not discount the presence of free HN3.
N4H4 is made by simple metathetic in liquid, solid, or gaseous media which may involve distillation or precipation. For example equimolar amounts of ammonium chloride and sodium azide may be distilled with an equal quantity of water. At 160C pot temperature, the product volatilizes with water vapours and solidifies in the condenser tube which should, therefore, be at least 1 inch wide. Equally clean and safe is a gas phase reaction which requires however, the preparation of hydrazoic acid gas. The reaction takes place in a long, 1-inch-wide glass tube which has 2 inlet tubes with orifices 20 inches apart, and a vent. The HN3 gas, carried with nitrogen, and excess ammonia stream in and precipitate the product as fine needles. N4H4 is also precipitated when ammonia gas is bubbled into an ethereal hydrazoic acid solution. The product stays in solution when HN3 vapours, carried with nitrogen, are bubbled into aqueous ammonia.
The following procedures have also been reported as advantageous, but are in fact inferior: Larger batches were made by mixing equimolar amounts of sodium azide and ammonium acetate as saturated solutions; upon cooling to 5C, N4H4 separated in a low yield(aprox 25%). Additional crystallizations from the mother liquor were contaminated with sodium acetate. Or, a distillation method uses dimethylformamide as a vehicle to react and distill sodium azide and ammonium sulfate. The procedure is cumbersome because of clogging of the condenser could not be controlled satisfactorally, in spite of elaborate equipment . not recommended is a dry method in which sodium azide and ammonium nitrate are heat treated , and the product is sublimed off at 200C. The vapour phase contains free HN3 which tends to explode above room temperature. Reportedly , 5g batches were made safely, but a 50g batch exploded at 158C.
Alkylammonium azides, such as the tetramethyl salt, [(CH3)4N]N3 are accessible through mixing the respective iodides with silver azide or, less hazardously, by neutralizing the respective hydroxides with hydrazoic acids to pH 8. Generally, they are more stable then ammonium azide, as free HN3 is not formed through dissociation. They burn in a flame without explosion and are insensitive to mechanical and thermal shock."
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The_Davster
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[*] posted on 9-5-2004 at 17:32


Quote:
Originally posted by BromicAcid
Does your book have any information on Aluminum tetraazidoborate Al[B(N3)4]3 ? All I have found on this compound is that it is a very shock sensitive explosive but it has always been somewhat intriguing to me.

There is no specific info on Aluminum tetraazidoborate but there is a bit on the tetrazidoborate ion
"The properties of tetraazidoborate resemble those of normal boron azide. It is synthesized , aparently in a 2-stage reaction, from lithium borohydride and hydrazoic acid.
LiBH4 +4HN3--> LiB(N3)4+ 4H2.
excess ethereal hydrazoic acid is condensed onto a frozen(liquid nitrogen) ethereal LiBH4. The solid mixture is allowed to warm up ; between -116 and -80C, H2 is evolved and LiN3 precipitates.
LiH.BH3+HN3 --> LiN3+BH3+ H2
near 0C, H2 is again evolved and ether soluble LiB(N3)4 is formed.
LiN3+BH3+3HN3--> LiB(N3)4 +3H2
After pumping the solvent off, the product is obtained as a white solid."
One could probally go from there to Aluminum tetraazidoborate.
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[*] posted on 9-5-2004 at 18:49
University


The more I hear about that wonderful place the more I am determined to get into one; even if its just to read the books. So much information; its like treasure!:D

Knowlage is power and if I get to a University then I will rise up and be more powerful than you can imagine!

Well someday;)

[Edited on 10-5-2004 by Quantum]




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[*] posted on 9-5-2004 at 19:22


When I went to that library there was rows and rows and rows of chem books. I am gonna live there in the summer.:P
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[*] posted on 10-5-2004 at 00:53
azides :o


I know that lead azide is made by mixing solutions of lead nitrate, sodium azide and dextrin and sodium azide is made by bubling nitrogen oxide throw molten sodium amide. My question is :
Are there any other ways to get sodium or hydrogen azide???
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[*] posted on 10-5-2004 at 01:44


I am fairly interested in azide compounds especially that of sodium azide and copper azide. Any extra info on that? What happens when they explode? Does the sodium azide form sodium and nitrogen gas?



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[*] posted on 10-5-2004 at 07:54


rogue, that is an interesting book you have!
I think I shall have a look in our big Uni library myself soon.... you may be surprised i have only been there once or twice, as all the biochem stuff is in the local library...

Anyway - does your book say anything about azides of organic amines? Methylamine, ethylenediamine, etc? how about hydrazine, or hydroxylamine?


PS hexogen, yes there are other ways, but similarly difficult. One is with hydrazine/nitrite.
The info is somewhere around here, I am sure.




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[*] posted on 10-5-2004 at 09:31


I wish you had a scanner ;) Anything on Mercuric Azide? Also does it have anything on organic azido binders e.g. Glycidyl Azide?
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[*] posted on 10-5-2004 at 15:26


Firstly, the sections on sodium, lead, copper and hydrogen azide are all about 10 pages long, too long for me to retype. I will try to get a friend to scan them and upload them somewhere.
Secondly:
"Hydrazine azide
Curtis made hydrazine azide, (NH2N5)N3 in 1891 from hydrazoic acid and hydrazine, both of which he had discovered in the two preceding years. Today, the compound has found application in rocket fuel technology.
N5H5 is a very hygroscopic, extremely soluble salt: at 23C, 100g water dissolve 190g. It also dissolves in methanol(6%) and ethano(1%); it is insoluble in ether. It is not sensitive to impact but explodes on heat shock; after melting at 70.5C it decomposes at about 90C. In a flame it burns without explosion. If hydrazoic acid is available, hydrazine azide is made by simple admixing the acid with an equimolar quantity of hydrazine, either by bubbling the HN3 gas or by using aqueous or ethereal HN3 solutions. In the latter case the hydrazine azide is precipitated. The preparation from sodium azide and hydrazine azide is more convienent. According to one source, 17g hydrazine sulfate, 17g sodium azide and 4g hydrazine are refluxed in 2L of n-butanol at 117C for 15min. The liquid phase is then separated and cooled to 5C when N5H5 is precipitated."

"Hydroxylamine azide
This compound, (NH3OH)N3 is made by neutralizing hydroxylamine with hydrazoic acid and is described as a white, volatile solid which is water soluble and melts at 66C."

Chemoleo, of the azides of organic amines, these were all that were in the book.
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[*] posted on 10-5-2004 at 15:29
Azides of mercury


"Azides of Mercury
Mercury(II) azide, Hg(N3)2 is a colorless, crystalline explosive which detonates with high brisiance on friction, impact and heat shock. Its explosive sensitivity depends largely on the particle form, of which 2 distinct types have been qualitatively described. The first consisting of compact, small crystallites of 60-80 um diam., is relatively insensitive and has without mishap been coarsely powdered or ground in nujol; it explodes on impact of a 500g weight dropping from 65mm. The second in the form of long thin needles, explodes at the slightest provocation or even spontaneously.
Hg(N3)2 is somewhat photo sensitive and turns yellow in bright daylight, owing to the appearance of colloidal mercury. It also decomposes thermally with gas evolution starting at 212C, followed by discoloration at 220C and explosion at 300C. The compound is slightly soluble in cold water(.257g in 100g solution at 20C); in hot water it dissolves more readily, without noticeable hydrolysis. It also dissolves in ethanolamine, apparently without chemical reaction, and in hydrofluoric acid, as a cation complex. Upon evaporation of the acid, the azide appears unchanged.
Hg(N3)2 has been made by dissolving mercury(II) oxide in hydrazoic acid
HgO + 2HN3 à Hg(N3)2 +H20
To separate the product from unreacted HgO, the azide is dissolved by heating and then filtered. It recrystallizes as the above mentioned, highly sensitive needles which have to be handled with extreme caution; eg., a large particle, slowly sinking in a water-filled beaker, exploded without touching the bottom. Likewise, crystals adhering to the wall could not be removed without explosion. It is essential to move the liquid constantly with a stirrer made of soft material, as slow cooling of an unstirred solution leads invariably to explosion.
The compact crystal form is prepared more safely by precipitating at room temperature a concentrated solution of mercury(II) nitrate or chloride with sodium azide. The product may be separated by centrifuging.
Among complex mercury(II) azides a colorless, explosive dipyridne diazido mercury(II) of the possible structure [HgII(Py)2(N3)2]0 is precipitated when water is added to a solution of mercury(II) nitrate in pyridine. A triazidomercurate(II) [HgII(N3)3)- is obtained from mercury(II) nitrate and excess sodium azide in acid media and isolated as the tetraphenylphosphonium salt.
Like mercury(II) azide, mercury(I) azide is a colorless, solid explosive, which is precipitated from aqueous media as a crystalline powder of high sensitivity. It explodes with high brisance on impact of a 500g weigh dropping from 60mm(lead azide,430mm; silver azide, 410mm). Heated at 283C it explodes in 178 seconds, and a 292C in 75 seconds. Slow thermal decomposition leads to discoloration at 170C and, melting with decomposition at 230C, and ignition at 400C. Its photo sensitivity is higher than that of mercury(II) azide: exposed to daylight it turns yellow, then orange, brown, black, and finally separates droplets of gray mercury. The mechanism does not involve disproportionation of the Hg(I) state.
Thin, crystal needles should be avoided as they are extremely sensitive, and would, upon breaking, set off the whole batch. Small particles are obtained by rapidly precipitating a concentrated mercury(I) nitrate solution with sodium azide and centrifuging the product."

Sorry Mongo Blongo, nothing on Glycidyl Azide.

[Edited on 10-5-2004 by rogue chemist]
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wink.gif posted on 11-5-2004 at 10:11


Thanks dude!:)
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[*] posted on 11-5-2004 at 10:34


Some info on hydrazinium azide hydrazinate [N2H5]+[N3]- . N2H4
from the Journal of Propellants, Explosives and Pyrotechnics.

Attachment: hydrazinium azide hydrazinate.pdf (87kB)
This file has been downloaded 4190 times





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[*] posted on 17-5-2004 at 12:23
Hydrazoic acid


I found an interesting route to NaN3 and HN3 from a old book called 'Van Nostrand's scientific encyclopoedia'
Word for word as follows;

Hydrazoic acid is formed (1) by reaction of ethyl or amyl nitrite in NaOH solution (sodium azide formed), then acidifying with dilute H2SO4 and distilling. Hydrazoic acid is recovered mainly in the early portion of the condensate, (2) by reaction of NH3 and Na metal heated to about 300 deg C. (sodamide formed) and then treating the residue with dry NO gas at about 200 deg C. The product is dissolved in water, then acidified and distilled as above. -brief but riveting!

Thought it would be worth sharing. The first method has my attention!




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[*] posted on 18-5-2004 at 06:02


Rougue Chemist, how about lead azide ? I made about 10 grams about two years ago and I'm curious about the storage problems. So far so good, but still...I heard about the recrystalisation in storage which tends to lead to bigger and less stable crystals.
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[*] posted on 18-5-2004 at 10:49


Quote:
Originally posted by froot
I found an interesting route to NaN3 and HN3 from a old book called 'Van Nostrand's scientific encyclopoedia'
Word for word as follows;

Hydrazoic acid is formed (1) by reaction of ethyl or amyl nitrite in NaOH solution (sodium azide formed), then acidifying with dilute H2SO4 and distilling. Hydrazoic acid is recovered mainly in the early portion of the condensate

I am sure that the first reaction is wrong. There needs to be hydrazine in there. Alkyl nitrite + NaOH just results in an alcohol and sodium nitrite.




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[*] posted on 18-5-2004 at 12:22


I thought as much.
Quite a nasty blooper for an encyclopoedia to have if that is wrong!




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[*] posted on 19-5-2004 at 14:30


Quote:
Originally posted by a_bab
Rougue Chemist, how about lead azide ? I made about 10 grams about two years ago and I'm curious about the storage problems. So far so good, but still...I heard about the recrystalisation in storage which tends to lead to bigger and less stable crystals.


I am getting my friend with a scanner to scan this section as it is too long to retype. I should have it here by the weekend. How do I upload to the scipics directory?
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[*] posted on 19-5-2004 at 14:46


Quote:
Originally posted by Polverone
Quote:
Originally posted by froot
I found an interesting route to NaN3 and HN3 from a old book called 'Van Nostrand's scientific encyclopoedia'
Word for word as follows;

Hydrazoic acid is formed (1) by reaction of ethyl or amyl nitrite in NaOH solution (sodium azide formed), then acidifying with dilute H2SO4 and distilling. Hydrazoic acid is recovered mainly in the early portion of the condensate

I am sure that the first reaction is wrong. There needs to be hydrazine in there. Alkyl nitrite + NaOH just results in an alcohol and sodium nitrite.


That might be a convenient synthesis for both sodium nitrite and isobutyl alcohol wouldnt it, if you were to use nitrite "poppers"? :)

if you were to omit the H2SO4 that is.

[Edited on 19-5-2004 by Lestat]

Any info on halogen azides? my rather unscientific guess is that I imagine they would be rather unstable, given the usual behaviour of azides. Do halogen azides exist at all?

[Edited on 20-5-2004 by Lestat]




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[*] posted on 1-6-2004 at 15:14


The info on lead azide has been uploaded to FTP2 under upload/rogue chemist/Lead azide. I would have put it in scipics but I dont know how:(.

Sodium azide files to come...
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[*] posted on 1-6-2004 at 16:18


Chlorazide N3Cl is described as a colorless very explosive gas obtained by the action of sodium hypochlorite solution and boric acide on sodium azide.

Iodazide N3I is a pale-yellow explosive solid obtained by the action of iodine on silver azide.

My old Textbook of Inorganic Chemistry also lists a number of other exotic azides: Cyanogen azide (CN-N3)2, sulphuryl azide N3-S02-N3 and azido-dithiocarbonic acid N3-CS-SH. But it doesn't mention any routes for synthesis.
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[*] posted on 1-6-2004 at 19:09


I really should not have returned that book to the library, when I go again next time I will look up the azides you mentioned, JustMe.
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