Sciencemadness Discussion Board

inorganic azides

vulture - 28-9-2002 at 11:00

Here's some info on various inorganic azides.

ammoniumazide, NH4N3 or N4H4, deflagrates faster than gunpowder when heated according to the following equation:

2NH3N3 -> 3N2 + H2 + 2NH3

Lithiumazide, LiN3, explodes with a loud bang when heated above 250C.

Azides of heavy metals like Ag, Cu, Pb and Hg detonate when heated or initiated by friction or shock.

Cadmiumazide, Cd(N3)2 is so sensitive that it will detonate extremely fiercely when scratched.

3Cd(N3)2 -> Cd3N2 + 8N2


The odd thing about azides is that no actual combustion occurs and the azide bond also doesn't store much energy. The sole responsible for the energy output is the formation of the triple bond in the N2 molecule which produces a large amount of energy.

Experiments trying to produce (N3)2 through electrolysation of HN3 with KN3 have failed.

The azide group can also be bonded to with chlorine and cyanide to form N3Cl and N3.CN respectively. Cyanicazide is prepared from brominecyanide and sodiumazide.
Cyanicazide explodes extremely violently when struck or when heated above 170C:

CN4 -> C + 2N2

A very interesting compound is azidothiocarbonicacid, which can be synthesized from sodiumazide and CS2.
Formula: SCN3Na.4H2O Explodes violently when heated in anhydrous form. The silver salt is easily initiated by weak friction.

organic and inorganic azides

BLAST_X - 29-9-2002 at 05:19

Hey hey,
it`s a old matter with this inorganic azides.
They had used sometimes as a primary
explosive many years ago [Pb(N2)3]
and nobody know other non-toxic
explosives with similar attributes.
Nowadays, they`re used to synthesized
more powerful organic azides.

for instance:
synthesis of hydrazinum azide [N2H5N3]
in a reaction of silver azide and hydrazinum iodide or
a reaction of anhydrous hydrazine and a mixture of hydrazoic acid and ehyl ether.

The peculiar characteristic feature of some azides
(ammonium azide, hydrazinum azide, ...),
they produces ammonia-gas after explosion.
A other important disadvantage of azides,
they`re extremely toxic (N3), therefore
they can`t use always.

organic and inorganic azides

BLAST_X - 29-9-2002 at 05:32

Sorry, the mistake in my last post.

The formula of lead azide of course
Pb(N3)2 !

vulture - 29-9-2002 at 05:36

Hydrazine is not an organic substance, so hydrazine azide falls under the anorganic azides too.;)

BLAST_X - 29-9-2002 at 11:06

I know,
it`s only a example for a new high energetic and highly toxic azide.

A example for a high energetic organic azide is ethanol azide,
(study of "Institute of Combustion & Advanced Technologies, Odessa State University")
or look at big group of aromatic azides.

organic azides

BLAST_X - 30-9-2002 at 05:04

If someone be interested in ethanol azide
as a energetic organic azide.
Here a little PDF.

Attachment: ethanol azide.pdf (103kB)
This file has been downloaded 1326 times


Azides

Voltforce - 4-10-2002 at 18:05

Azides are really interesting. I was going to synthesize lead azide, but the local chemical supplier shut down. Too bad (N3)2 can not exist! If it did exist, it would probably be an unstable poisonous gas.

PHILOU Zrealone - 3-3-2003 at 08:27

Two of the most interesting azides are
Cyanuric triazide (C3N3(N3)3)
Triazidotrinitrobenzene (C6(N3)3(NO2)3)
High density, relatively stable, impact sensitive (but not too much) and powerfull!
Can be dead pressed and are used as primers secondary charge!

Other organic and inorganic azides!

CH3-CO-N3 treacherously explosive

Al(N3)3 may detonate by shock

NH4N3 explodes on rapid heating

N3-CH2-CH=O decompose vigorously at 80°c under 5 mbars

N3-CH2-CO-CH3 exploded after 6 month in the dark

N3-CH2-C(=NOH)-CH3 (exploded violently on distillation of residue)

(CH3)2N-N3 (rather explosive)

(CH3)2B-N3 (explodes on warming)

5-azidotetrazole and its salts are explosives

Ba(N3)2 impact sensitive when dry

C6H5-SO2-N3 decomposed smoothly when pure at 105°C but explodes when crude

C6H5-CO-N3 crude explode violently between 120 and 165°C

Br-N3 very shock sensitive in all physical states, explodes on contact with As, Na, Ag, P, ...

(CH3)3C-O2C-N3 exploded on distillation at 74°C and 92 mbar

(CH3)3C-O2C-CH(N3)2 distillation under vaccuum potentially hazardous

Cd(N3)2 dry solid explodes on heat, light friction, even in standing solution spontaneous explosion may occur!

Ca(N3)2 explodes arround 150°C

(N3)2C=O violently explosive solid, usable only in solution!

Cl-N3 extremely unstable, explodes without causes

Cl-CrO3-N3 explosive solid

CH3-SiH(N3)2 old sample exploded

N3-CH2-CH2-N3 explosive

(HO2C)2C(N3)2 shock sensitive explodes wihout warning

N3-CH2-CH2-CH2-N3 exploded while being weighted

N3-S-S-N3 explodes below 80°C with dilute NaOH an explosive deposit is formed under 0°C

CH3-CH2-N3 may detonate on rapid heating!

CH3-CH2-O2C-N3 liable to explode at 114°C

F-N3 unstable explodes on vapourisation at -82°C

Glutary diazide may explode on heating

HN3 safe in dilute solutions, violently explosive when conc or pure.

I-N3 shock and friction sensitive explosive

Pb(N3)2 detonator well known primary.Prolonged contact with Zn or Cu forms extremely sensitive azides.

Pb(N3)4 liable to spontaneous decomposition sometimes explosive

LiN3 moist or dry salt explodes at 115-298°C depending on heating rate!

Hg2(N3)2 explodes arround 270°C.

CH3-N3 stable at room T but may detonate on rapid heating

C6H2(NO2)3N3 explodes weakly on impact

Pivaloyl azide explodes on warming

KN3 melts on heating then evolves N2 and residue explodes weakly. explodes at 120°C

Si(N3)4 spontaneously explosive from time to time

NaN3 decomposed somewhat explosively above its mp

NaOSO2-N3 weak explosive of variable sensitivities!

Succinoyl diazide exploded during isolation

S(N3)2 explodes violently when heated and sometimes spontaneously at ambiant T

Tl(N3)3 relatively stable, it can be exploded on heavy impact or by heating at 350-400°C

C3N3(N3)3 explodes on impact, shock or rapid heating to 170-180°C

Madog - 4-3-2003 at 16:11

awsome post, the triazidodinitrobenzene reminds me of an idea i had the other day while eating dinner. azidotrinitrobenzene. i was thinking this could be made by makeing a halotrnitrobenzene from TNT then reaction it with NaN3. does anyone know if the reaction with the NaN3 would go through easy? this link makes me think not

http://www.rhodium.ws/chemistry/mda.azide.html

im guessing that other chemical in there is a catylist

PHILOU Zrealone - 23-3-2003 at 14:42

It is a Sanger reaction (aromatic electrophilic substitution)!

Ex:
Cl-C6H2(NO2)3 + NaOH --> HO-C6H2(NO2)3
Cl-C6H2(NO2)3 + NH3 --> NH2-C6H2(NO2)3 + NH4Cl
Cl-C6H2(NO2)3 + NaN3 --> N3-C6H2(NO2)3 + NaCl
Cl-C6H2(NO2)3 + CH3-OH --> CH3-O-C6H2(NO2)3 + HCl

Cl(-) is a very good leaving group when in ortho or para of an electron withdrawing group!

See the making of TATNB from TrichloroTNB, the same way is used to make TAzTNB!

:cool::o:):D;):P

PHILOU Zrealone - 24-3-2003 at 10:41

Damn I was really tirred:
Sangers reaction is a NUCLEOPHILIC aromatic substitution!Actually many other nuclophiles can be used instead of
H-O-H
CH3-O-H
Na-O-H
NH2-H
You of course may use:
CH3-NH-H
NH2-NH-H
NH2-CO-NH-H
CH3-S-H
Na-S-H
...
You soon see the valuable interest of chlorobenzen via dinitro or trinitro derivatives to give a bunch of chemicals of all nature!

:cool:

AndersHoveland - 6-1-2013 at 16:18

Lithium azide has only moderate explosive properties. Decomposition of lithium azide only forms lithium nitride and nitrogen. It can survive hammer blows without detonation.

Sodium azide is not an explosive. (probably explained by the fact that sodium nitride is not very stable, decomposing into its elements at only 87 °C ) None of the other alkali methal azides are explosive either, although rapid heating can lead to violent decomposition into nitrogen gas and the reactive alkali metal in its elemental state.

Calcium azide begins to thermally decompose above 110 °C, and explodes at 158°, it is more explosive than either strontium or barium azide.

Barium azide is a sensitive explosive, with a drop height value of 10cm. It appears to be relatively insensitive to impact but highly sensitive to friction.
H. Ficheroulle, Mem. des Poudres. 33, 7 (1956)
The temperature at which barium azide explodes is apparently highly variable, values have been reported between 152° to 221°C. The enthalpy of formation for barium azide from its elements is actually slightly negative, -5.3 kcal/mole. The formation of barium nitride is very favorable, the compound having an enthalpy of formation of -89.9 kcal/mole. The decomposition of barium azide tends to form barium nitride, although some elemental barium is also forms.
"Nitrogen Burning of Metals", G. Petrov, Combustion, Explosion, and Shock Waves, Volume 11, Number 3, 309-312


Hydrazoic acid can act as either an oxidizing agent or reducing agent. For example, it reacts with copper according to the following equation:
(3)HN3 + Cu --> Cu(N3)2 + NH3 + N2

[Edited on 7-1-2013 by AndersHoveland]