Sciencemadness Discussion Board

Stabilizing Nitrogen Tri-iodide

DeusExMachina - 13-2-2003 at 10:45

I searched on this a little and even if I did findd sometihng, I was still going to ask to get an input from you guys. I would like to know if there is a way to stabilize nitrogen tri-iodide. I heard that to make it less sensitive when it is wet, it needs more ammonia but I am not very concerned with that. I would like to know if there is a way to handle nitrogen tri-iodide safely. Well, is there?

Blind Angel - 13-2-2003 at 13:30

my chemistery knowledge aren't the highest but maybe mixing it with something solid like Styrofoam + Gaz (dunno the real name in English sorry) would help?

DeusExMachina - 13-2-2003 at 16:07

that's a crappy (I don't even know if it's real) napalm. That's what I'm saying... you cant mix it.... if a little fly goes on it, it'll detonate. I'm asking if there is anything that can be added while you are making it.

a_bab - 13-2-2003 at 17:25

You can's stabilize it. It'll decompose really fast and even when wet it can explode. I had an accident involving NI3 when some exploded under water ! the beaker was turned into dust. I wasn't there, but I was worried about the neighbours, because the explosion was loud. That day was one od the worse in my life, expecting the pigs due to a reclamation...It wasn't the case though.

Still there is some document which describes quite a lot of interesting things about how to make it, or how to keep it. The author used some starch to decrease it's sensitivity.

Darkfire - 13-2-2003 at 18:17

I HIGHLY sugest you dont do NI3 dues, you need much more knowage on explosives and general chemistry before even apemting ni3, there is no way to stablise it; only thing that might come close is adding activate carbon to the nutralised ni3 bearing solution to help reduce the chance of predetonation, thats only a geuss so dont quote me on it.

CTR

Ramiel - 14-2-2003 at 18:30

I have found that if it is still wet with an ammonia solution, or the crystals are not dry, it is considerably harder to detonate (i was stomping on it, and it wouldn't go off). You may have problems with this method, however, since it is also my experience that the crystals dry out easily within 24 hours at ~50% humidity and room temp.

Don't make 'em. I get sick to the stomach these days if i even smell the stuff.

DeusExMachina - 16-2-2003 at 14:54

I wasn't going to make it anyways. It'd be stupid to make it. If someone wants something thats easy to make and isn't too sensitive, they should go for AP.

Microtek - 16-2-2003 at 23:44

Yes nitrogen iodide is a very poor candidate; first and foremost because of the sensitivity of course, but also because it is not very powerful. I suppose you all know the demonstration experiment for showing the sensitivity of NI3, where a feather is used to set off the compound ?
Well, they have showed us that experiment a couple of times at my university and each time they have filtered the wet NI3 through ordinary filter-paper on a plastic funnel mounted in a clamp. Then when the material had dried sufficiently, they touched it with the feather-on-pole thing to cause detonation. In each case I have noted that the plastic funnel was undamaged by the explosion, which wouldn't have been the case had it contained HMTD or other common types of explosive.

a_bab - 17-2-2003 at 11:41

Maybe that was due to the fact that the NI3 was slightly damp. I found that if damp it's power is very low. It can bearly tear the filter paper.

DeusExMachina - 18-2-2003 at 09:14

so it would be safe to detonate whith small amounts when it is damp with ammonia right? I might try that...

madscientist - 18-2-2003 at 17:29

It's not safe when wet. Only less dangerous.

Be wary of iodine gas. Our biology doesn't appreciate its presence in quantities beyond what is found in iodized table salt.

DeusExMachina - 18-2-2003 at 20:56

so how poisinous is the iodine gas?and compared to AP, how strong is it?

nitrohalogens

mitch77 - 19-2-2003 at 16:06

This is my first post, so I’ll get right to it. Very interesting discussions by the way.

First off, this post is of my observations, your mileage may vary. Having made this stuff innumerable times, the best way (i've found) to get a decent yield outside of a well-equipped lab is:

1. Get a beaker full of regular (clear and not perfumed) ammonia water from the store, and some iodine crystals. Not the tincture of iodine. This might be the hardest part to obtain, at least in the US, because it’s a watched precursor for some illegal drug synths... though they watch HI traffic much more carefully.

3. Take a quarter teaspoonful of iodine crystals crushed well and drop it into the ammonia water. Now let it set for a bit, say 30 minutes. Be sure to cover the container with a glass plate or at least saran-wrap. This boosts the yield (greater concentration of ammonia), and improves stability because the formed nitrogen triiodide is more stable in the aqueous ammonia). Avoid the highly concentrated and not worth the aggravation.

4. Pour out most of the water, but don’t decant all the water until the very end! It’s important to keep the nitrogen triiodide saturated with the solution. Leave enough ammonia so the crystals are covered in the container at all times.

5. Scatter the sludge at the bottom of the contained about the place. Do not touch dry material! Even if the smallest crystal on the rim of the beaker that dries out can detonate the whole batch. Use a popsicle stick to scrape the goodie from the bottom of the container.

6. Take your container a place you where you can wash it out. The rinse water contains a lot of triiodide scraps so dispose of the liquid in a clever way. When the solid you set explodes (upon drying), it will make a lot of iodine gas that should be avoided. Also it is much louder than you think so be smart. Clean your hands if necessary with thiosulfate solution.

Evidently the formula for the substance is NI3.xNH3 where x is a function of the temperature. I believe the x ranges from 0 at higher temperatures to 8 or so at very low temps. Don’t know if that affects the efficacy of the desired product one way or the other. My opinion, given the behavior of the tribromide, that the greater the x the more stable the substance. This would corroborate its stability in a solution of NH3 too. I get much more satisfying noise in the summer months, btw.

Oh and about keeping it stable for any length of time… I remember reading of an experiment done by a guy who impregnated gelatin with the triiodide in an attempt to use the gel to prop up those jittery molecules. I think he only succeeded in prolonging its life by a few hours.

Back into the darkness. Pax.

DeusExMachina - 21-2-2003 at 09:34

ok, by scraping it or even touching it with something, it will detonate. I need your help guys. I've searched a little and I didn't really find anything. I'm not a very good searcher so maybe you guys can help me out a little.

Thanks!

PHILOU Zrealone - 19-3-2003 at 08:27

I woul suggest very tiny amount (I have made on purpose a 5g batch and detonated it dry by lifting up the filter paper very carefully and let it fall on the ground!Damn my ears were ringing strong!

I also did a test in the lab at university (we used to make fun things while waiting our experiments to end); playing with liquid N2, make minute lemon ice, NH3NI3!
Then when I had the wet stuff I putted some on the ground where a friend was walking (there was only 2 mg but the noise it made without leaving a trace made the guy jump 1 meter high and watching all arround (Too funny)!
Anyway he asked what it was and I had made a second bobytrap one 0,7cm ball was putted 10 cm away from a 0,4cm ball itself at 10 cm from a third 0,2 cm and next to that a flat spot 10 cm... I asked him to snatch the tiny spot with his shoes and he said:"hey it doesn't wor BOOOOOOM TUUUUUUUUUUUUT" the tiny spot had detonated sympathetically with all the surrounded spots (maybe via sound propagation wave in the ground or via air blow) all the lab was alarmed, all the students came to see what happened, even the teachers and students from next lab behind the scaleroom...too funy to see we were the only one to work!
There was no trace of anything left so noone to incriminate for nothing but a big noise!

Never underestimate the power and the sensitivity of this stuff; it should be handled only in less than 1 g at the time (a pea size ball).

I know that a slightly stablest form can be made from the complexating media using iodide salt with solid I2 (in iodide solution I2 dissolves very well)!
NH4I/I2 + NH4OH
Then with time and by evaporation you get purple cristalls (no black mess)!
Beware of large cristalls!

By the attempt using gelatin, the guy was able to bring a very large batch on a blast site a few miles away; but I wouldn't handle a large batch of this even if it seems stable!
Things can go bad too fast with this shit!
:o :o :o :p :p :p
NH3NI3 has been detonated from ultrasounds at distance; so does Hg fulminate!

stabilizing NI3

the timeless - 8-9-2003 at 23:00

I think I have heard that it could be stabilized with corn starch or syrup. This procedure reduces the friction between the NI3 chrystals and therefore reduces the danger. For example the detonation in the famous feather test is caused by this match-strike effect not the pressure caused by the feather.

markx - 9-9-2003 at 04:51

Would not be very advisable to mess around with that stuff- too unpredictable, too sensitive!!
We prepared a small demonstrative batch for sophomores and left it to dry on the lab table and it detonated from the sound of closing the lab door that was good 5m away.
And it was wet- freshly prepared... make your own conclusions but I'm staying the hell away of that stuff!!!

sylla - 10-9-2003 at 13:03

This could be interresing for those who don't have access to pure iodine. I haven't test it yet but I think it should work... If someone has the time to test it... =)

I'm not sure that the reaction will go and I'm not sure that iodine could easily be removed from the solution

H2O2 + 2KI + 2HCl -> 2H2O + 2KCl +I2

I'm quite newbie in chemistry but I know that anyone can purchase KI or KIO3.

If I'm wrong please tell me

asterlite - 11-9-2003 at 08:07

how about concentrating the I from betadine solution?

vulture - 11-9-2003 at 09:23

H2O2 + 2KI + 2HCl -> 2H2O + 2KCl +I2

This may work because you'll be producing chlorine which displaces the iodine.

Easier is if you use another acid that doesn't react with H2O2.

AndersHoveland - 20-3-2013 at 18:12

Perhaps if a 2:1 molar ratio of NH4OH to ethylene diamine was used. I suspect that a compound like
NI3-NH2-CH2-CH2-NH2-NI3
would form, and might be a little more stable than ordinary "nitrogen triiodide".

At least with the reaction between chlorine and ammonia, it is known to be an equilibrium reaction (although within a certain pH range and given enough time, the ammonia can be irreversibly oxidized to N2).

I suspect the compound "nitrogen triiodide", NH3*NI3, is actually an adduct.

NCl3 may not be able to act as a lewis acid in the same way because the iodine atoms have much bigger atomic orbitals to accomodate the extra charge.

While ethylene diamine can react with Cl2 to form an explosive, I think that it would not be iodinated in this situation because the equilibrium would not favor it. NI3 would act as a much better lewis acid, leaving the ethylene diamine as the lewis base.

The fact that real NI3 cannot be obtained from I2 and NH4OH is not surprising. The NH3 is bound as an adduct and rendered unreactive to further attack by additional iodine. Cl2 cannot oxidize ammonium ions either in acidic solution (although some NCl3 can be formed from NH4Cl in dilute aqeous solution, presumably because there is some dissociation of the NH4Cl into NH3 in the solution)

Sorry, it is really a very complicated topic, and it seems impossible to fully explain without going off topic.

Actually the NI3 groups ( in NH3*NI3 ) are cross polymerized into a linear chain through the iodine atoms, not surprising since the triiodide ion also exists (which is why KI greatly increases the solubility of iodine in water).

[Edited on 21-3-2013 by AndersHoveland]

AJKOER - 21-3-2013 at 10:24

I think it is hard to generalized as to whether double salts of unstable compounds are more stable. I just cited in a fulminate thread a reference (see http://www.dtic.mil/dtic/tr/fulltext/u2/625397.pdf ) where certain double salts were generally considered by the author as more sensitive/unstable. To quote: "Double salts of the alkali fulminates with mercuric fulminate are even more sensitive." Now, in the case of dry NI3.xNH3, increased sensitivity is really hard to imagine for anyone acquainted with the salt.



[Edited on 21-3-2013 by AJKOER]

Motherload - 21-3-2013 at 21:34

What do you plan on achieving by stabilizing NI3 ?
It will never be considered a reliable primary .... Especially when there is a wack to choose from.
It can only be used for pranks etc.
in which case you can just paint it on when wet.

franklyn - 22-3-2013 at 08:18

Another related thread on NI3
www.sciencemadness.org/talk/viewthread.php?tid=3905

Nitrogen Triiodide
I. C. Tornieporth-Oetting, T. M. Klapötke,
Chemical & Engineering News 1995, 73(46), 4.

___________________________________


The other trihaloamine
www.sciencemadness.org/talk/viewthread.php?tid=2079

NCl3 being fluid is inherently less sensitive to mechanical disturbance
but is chemically reactive making it unexpectedly sensitive.

The same way that nitric esters are rendered safer for use as dynamites
is to absorb them into diatomaceous earth or synthetic zeolites.
www.soapgoods.com/product_info.php?products_id=1003

I would guess that the same principle can apply with NCl3
if admixed after with something that will coat the particle
surface to isolate the NCl3 from chemical reactions.

___________________________________


Elementary precautions taken by early investigators has
been to dilute NCl3 in solvents such as carbon tetrachloride.
Evaporation would restore the pure material. It appears
Methylene Chloride can potentially be an explosive mixture.
CH2Cl2 + 2 NCl3 => 2 HCl + CCl4 + N2 + Cl2

Other solvents may similarly serve as fuel.

___________________________________


The notion of formulation compounding of trihaloamines is
novel in this forum , at least this is the first suggestion of it.
The prospect of a Nitrogen Trichloride Coordination Complex
is unexplored. Perhaps with Copper Chloride or Zinc Chloride.

Thoughts ?

.

AJKOER - 7-8-2019 at 06:20

Quote: Originally posted by DeusExMachina  
I searched on this a little and even if I did findd sometihng, I was still going to ask to get an input from you guys. I would like to know if there is a way to stabilize nitrogen tri-iodide. I heard that to make it less sensitive when it is wet, it needs more ammonia but I am not very concerned with that. I would like to know if there is a way to handle nitrogen tri-iodide safely. Well, is there?


To answer the question if there is a way to handle NI3.NH3 safely, the answer appears to be yes!

Per an old chemical journal (per an extract in Atomistry.com on NI3 at http://nitrogen.atomistry.com/nitrogen_iodide.html ) to quote:

"The reaction between iodine and ammonia appears to proceed in three stages. Firstly, hypoiodous acid and ammonium iodide are produced:

NH4OH + I2 = HOI + NH4I;

and the hypoiodous acid further combines with ammonia to form ammonium hypoiodite:

NH4OH + HOI = NH4IO + H2O.

Finally, the ammonium hypoiodite decomposes into nitrogen iodide:

3NH4IO ⇔ N2H3I3 + NH4OH + 2H2O.

The last reaction is apparently reversible, as the nitrogen iodide redissolves in strong ammonia."

By the last statement, which appears to be supported elsewhere, for example, per Wikipedia (https://en.m.wikipedia.org/wiki/Nitrogen_triiodide ) to quote:

"When kept cold in the dark and damp with ammonia, NI3 · NH3 is stable."

And, per another source (see http://www.acornusers.org/education/Thesis/NI3andAgar.html ):

"When the NI3 is in the presence of ammonia solution, it is very stable for transportation and study. When the ammonical solution is removed, the amount of energy keeping the adduct together is too small, so the ammonia evaporates off, leaving the highly unstable solid."

with one possible explanation that, in the presence of strong ammonia and water (causing it to dissolve), it is no longer chemically NI3 · NH3 !

However, I do believe the Wiki statement is remiss in not citing concentrated ammonia presence, while the second statement does at least account for the potential danger in dilute aqueous conditions from the loss ammonia. There is one report suggesting the detonation of a large amount of aqueous NI3.NH3 (I surmise from the likely loss of ammonia) in wet conditions! Here is an extract from another SM thread supporting this report (at http://www.sciencemadness.org/talk/viewthread.php?tid=16208 which also contains one of the most detailed prep I found by GreenD):
Quote: Originally posted by spotlightman1234  
You never want to wash NI3 with water or any other solvent!! nitrogen triiodide forms an adduct with ammonia
NI3-NH3-NI3-NH3.... this is why the nitrogen triodide is stable when wet in ammonia, but when it is allowed to dry the ammonia leaves, leaving only NI3.. I tested this by (from a distance of course) washing wet NI3 with water to get rid of the ammonia. After about 200ml of water were washed through the filter paper some of the NI3 exploded, spreading NI3 everywhere making a fun residual crackling sound.


Not sure if I agree with the suggested chemistry by Spotlightman1234 as the dry salt, per the ammonia path, is NI3.NH3, as long ago, it has been decomposed to largely indicate a compound formula of N2H3I3 (or, at least some hydrogen, see https://books.google.com/books?id=1iQ7AQAAMAAJ&pg=PA539&... ). However, I would suggest that isolated breakage of the NI3.NH3 chain, exposing unstable NI3, occurring more frequently in low NH3 concentrations, is a possible explanation, along with the alternative suggestion for creation of the unstable, but not explosive, NH4IO, or my personal choice, a movement of the equilibrium to favoring NHI2.

The absence of light is also important given the general sensitivity iodide salts to light (causing a breaking down into atomic iodine, and some I2 created therefrom).

Rapid removal (as a path to detonation) of the NH3/H2O could be accomplished with, say, dry CaCl2, which also removes NH3 with the formation of CaCl2.xNH3.

[Edited on 8-8-2019 by AJKOER]

twelti - 7-8-2019 at 08:23

My own experience suggests that if there is enough NI3 in the container, the material at the bottom may dry out enough to detonate. I had this happen when I was a wee lad. I had it in a test tube, around maybe an inch of it. I tapped the bottom of the tube and the stuff on the bottom detonated. The stuff on the top just sprayed all over the room and then started quickly drying (due to ammonia evaporating). My dad was due home from work in 20 minutes, and I had small bits of NI3 all over the bathroom, and some starting to detonate! I wish I could go back and watch my reaction.

Morgan - 7-8-2019 at 13:02

I remember a method described in the book Chemical Magic where they used potassium iodide and wondered if the salt would have any affect on the sensitivity?

Action:
Walking into a room, a person is startled by sharp crack-
ling sounds at his feet as he steps on small pieces of paper.
Touching the paper lightly with a meter stick brings about
small but sharp explosions.
You Need:
Five grams iodine; three grams potassium iodide; 20
ml. concentrated ammonium hydroxide; filter paper;
funnel.
Why:
Nitrogen triiodide when dry explodes with the slightest
disturbance.
How:
Stir the potassium iodide and iodine together in a beaker
with 50 ml. of water. Add the ammonium hydroxide with
stirring until no more precipitate forms. Filter and spread
a thin layer of the wet solid on several filter papers. Break
the filter papers into many small pieces and allow to dry for
several hours.
On drying, the paper is extremely sensitive to touch and
will explode violently with the slightest disturbance.
Caution:
The compound nitrogen triiodide, NH3.N!:1, can be safely
handled when wet. Spreading a thin layer of the wet material
on several pieces of filter paper lessens the violence of each
explosion. It is not a powerful explosive, rather a sensitive
one. The touch of a feather can set it off. UNDER NO CON-
DITION ALLOW ANY SIZEABLE QUANTITY OF THE
DRY MATERIAL TO ACCUMULATE.

AJKOER - 6-6-2020 at 05:34

Actually, I conceived of a path to not only stabilize but possibly further turn the composition into a very problematic dangerous HE as well.

So, take this as advice more on the side of never perform this experiment even in what you suspect is but a tiny crystal of dry elemental Iodine. If one were to place dry I2 on a flat sheet of say Al foil resting on a pile of damp/wet NH4Cl, a seemingly stable situation (there is nothing inherently explosive here).

However, on slow warming in a closed vessel so that:

NH4Cl (s) + H2O (l) + Heat = NH3 (g) + HCl (g) + H2O (g)

I2 (s) + Heat -> I2 (g)

And then possibly:

3 I2 + 4 NH3 -H2O-> 2 NI3.NH3

3 HCl + NI3.NH3 -H2O-> Products (may include NCl3, see below)

2 NCl3 -> N2 + 3 Cl2 + Energy

I suspect the presence of water is required as it has been reported:

NI3 + 3 HCl = 3 ICl + NH3 (see https://books.google.com/books?id=e0RFAQAAMAAJ&pg=PA93&a...)

And as:

ICl + H2O = HOI + HCl

NH3 + HOI = NH2I + H2O

NH2I + HOI = NHI2 + H2O

NHI2 + HOI = NI3 + H2O (generally cited path to NI3.NH3)

Expect also, however:

3 HOI -> 2 HI + HIO3

HIO3 + 5 HCl (g) -> 1/2 I2 + 5/2 Cl2 (g) + 3 H2O (see https://chemiday.com/en/reaction/3-1-0-6123 )

And, as the action of Cl2 on aqueous NH4Cl is a cited pass to NCl3, I would not dismiss it possible formation here as well.

So, if the system on heating demonstrates higher energetics, then my supposition of the above reaction products (to a limited extent) is likely affirmed.

[Edited on 6-6-2020 by AJKOER]