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The_Davster
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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.
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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halogen
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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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The_Davster
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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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BromicAcid
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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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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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| 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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Quantum
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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!
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]
What if, what is isn\'t true?
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The_Davster
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When I went to that library there was rows and rows and rows of chem books. I am gonna live there in the summer.
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heksogen
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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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darkflame89
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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?
Ignis ubique latet, naturam amplectitur omnem.
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chemoleo
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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.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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Mongo Blongo
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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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The_Davster
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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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The_Davster
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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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Mongo Blongo
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Thanks dude!
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vulture
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Some info on hydrazinium azide hydrazinate
[N<sub>2</sub>H<sub>5</sub>]<sup>+</sup>[N<sub>3</sub>]<sup>-</sup> .
N<sub>2</sub>H<sub>4</sub>
from the Journal of Propellants, Explosives and Pyrotechnics.
Attachment: hydrazinium azide hydrazinate.pdf (87kB)
This file has been downloaded 6177 times
One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
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froot
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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!
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
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a_bab
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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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Polverone
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| 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.
PGP Key and corresponding e-mail address
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froot
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I thought as much.
Quite a nasty blooper for an encyclopoedia to have if that is wrong!
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
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The_Davster
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| 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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Lestat
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| 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.
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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]
The meek arn\'t going to inherit everything, their greedy relatives will get there long before someone bothered to tell the meek than someone has
died.
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The_Davster
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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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JustMe
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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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The_Davster
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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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