Nitrogen Trichloride

[endotherm]

<a href="http://roguesci.org/megalomania/explo/nitrogen_chloride.html" target="_blank">Nitrogen Trichloride</a> is an oily yellow high explosive. It's ease of manufacture and availability of needed precursors have sparked my interest in this explosive. It is said to be impractically insensitive, but the same is said of Acetone Peroxide, and many forum members have found it to be a sensitive, but useable compound. Has anyone had any experience with Nitrogen Trichloride, does anyone with a big set of nuts wanna take a go at it, and report the results?

[Mr Cool]

Nitrogen trichloride has no use. It's just as nasty to handle as nitrogen triiodide.
But hey, make it if you want. Just think: What do you want more - nitrogen trichloride or fingers?

[nbk2000]

As pyros, we've all accepted the risk of death or maiming from explosions, so it's just a matter of risk acceptance and reduction.

I've been interested in NCl3 too, because it's just all around nastiness. It's very toxic, corrosive, explosive, and decomposes into a toxic gas (chlorine) upon explosion.

It is easily made from readily available materials so that's a big plus.

The downside is it's ability to explode from bright light, dust, and other "gotcha!" means. I'd say, since it's very similiar to NI3, that's it's just as sensitive.

So, while I'd like to try it, it's not worth the risk to me, except in very small (gram or two) quantities. Unless you come up with a way to make it in situ at the target site, or a suitable solvent to desensitize it.

[a_bab]

In fact is EXTREMLY sensitive. ANY organic substance in TRACES will decompose it with an explosion. For it's study the scientists used solutions of NCl₃.

There is a thread somewhere with an NCl₃ accident, described by Vasia Pupkin.

[Pu239 Stuchtiger]

You, my friend, belong here. <a href="http://madsemail.netfirms.com/cgi-bin/yabb/YaBB.cgi" target="_blank">http://madsemail.netfirms.com/cgi-bin/yabb/YaBB.cgi</a>

[endotherm]

Pu239 Stuchtiger, was that addressed at me? And if so, can i have an explanation?

+++++++++++++++++++++++++++++++++++++++

It wasn't directed at you, but rather a k3wl who's posts I've deleted from this topic. I left Pu239's link up for our amusement.

Sorry for the possible misunderstanding.

NBK

<small>[ April 06, 2002, 11:07 PM: Message edited by: nbk2000 ]</small>

[firebreether]

omg, that link was probably the funniest thing ive ever seen all weekend! nice idea NBK to leave it up for our amusement;)

[inferno]

Given the sensitivity of NI3 and chlorine, it would probably be as sensitive as NI3. Im not a chemist, but thats just how i see it, logically.

[vulture]

Hmm, seems like NCl3 was formerly used for bleaching corn, but it has been forbidden because of the formation of toxic organic compounds. If it has been used this way it shouldn't be that sensitive...

Doh! Ofcourse.....stupid me...(see below)

<small>[ December 15, 2002, 05:27 PM: Message edited by: vulture ]</small>

[nbk2000]

That sit eis a parody site ran by a member here. It's just a joke, not some actual k3wl site. Though there are plenty of them like that that are real.

As for the NCl3 being used for corn sterilizing, it was generated in situ by some chemical reaction, not manufactured and shipped from some factory.

[xyz]

Soeone said that for research, solutions of NCl3 are used. What could be used to dissolve it?

Edit:Assuming it wasn't water :)

<small>[ May 30, 2002, 05:18 AM: Message edited by: xyz ]</small>

[Mr Cool]

Probably any chloroalkane, e.g. methylene dichloride.

[X-Wulf]

Assuming that the method used in NCl3 synthesis is to bubble gaseous Cl2 through aqueous NH4NO3, could someone please help in identifying which of the following equations represents what actually occurs:

Either A:
2NH4NO3 + 5Cl2 -&gt; 2NCl3 + 2NO2 + 2H2O + 4HCl

or B:
NH4NO3 + 3Cl2 -&gt; NCl3 + HNO3 + 3HCl

Has anyone actually prepared pure NCL3? Because the yellow colour could be attributed to the NO2 (if eqn. A is correct), or the yellow colour and sensitivity to light could be attributed to HNO3 (if eqn. B is correct). Either way you swing the cat, I see a lot of acid being produced, and that is very seldom a good thing to have around explosives.

No doubt NCL3 does share sensitivity likenesses with it's halo-brother NI3, but the presence of acid (especially HNO3) and nitrous oxides could be severely aggrevating the problem.

Sorry if this post sounds like an exam paper, I just finished writing chem. finals, and as such any input from the more experienced and educated forum members would be greatly appreciated.

Edited for spelling.

<small>[ November 15, 2002, 12:41 PM: Message edited by: X-Wulf ]</small>

[drednort]

NCl3 is an unpredictable substance probably moreso than NI3. It was first made in 19th century but the guy studying it lost 3 fingers and an eye for his trouble. It can be used in solution however, chlorinated or etheral solution. Water will decompose it

NCl3 + 3H2O -&gt; NH3 + 3HOCl (bleach)

It is made industrially by electrolysing NH4Cl under acidic conditions. The gas (NCl3) produced is removed using a stream of air and used immediately.

[vulture]

I suspect that NCl3 is somewhat more stable than NI3 because of the much smaller atom radius of Cl. THis means the bonds should be somewhat stronger. Ofcourse, if it shows the nasty habit like other chlorine compounds to react in presence of UV light, then you're fucked anyways.

[drednort]

these nitrogen trihalides are rather peculiar substances. NCl3 is quite unpredictable, NBr3 explodes even at -100oC, NI3 is actually an ammonia adduct [NI3.NH3] and probably derives some stability from this. The only stable one is NF3, which is pretty much unreactive to most things ... water, dilute acids and bases. It will flourinate things at high temperatures, though.

-yeah it makes sense that the shorter bonds give stability. Probably the reason that pure NI3 has never been made.

[Bo bo]

Reading through my 1910 inorganic text book it outlines a method for producing NCl3 by inverting a jar filled with chloine into a saturated solution of NH4Cl and collecting the oily droplets formed on the edges of the jar.

It is stated as 'The most explosive substance known'(not sure whether that means sensitivity or actual brisiance) and for curriosity purposes only.

[Marvin]

Suggestion, something that works better as a general principle, dont try to deduce how unstable a reactant is, try looking for how stable the corrisponding product is.

NCl3 is more stable in acid, where its formed from the ammonium salt of any strong acid, NI3.NH3, a polymeric adduct, is more stable in alkaline conditions, where its formed. The latters sensitivity depends mostly on how much ammonia its lost, so it varies wildly. Fundamentally NCl3 is liquid though and so it allready has a massive head start compaired to most solid explosives, cf liquid vs frozen NG.

In the times it was studied pure, containers were cleaned very carefully with sodium hydroxide solution first, its been known to go off as a result of a fingerprint on the glass. Inorg. Synthesis has a method of producing it as a solution in carbon tet (I think), but its states the solution evolves phosgene slowly on keeping, which only leads me to wonder from what reaction the oxygen comes from. This solution is stated to be completely safe frome explosion, but this is the same series that advises production of barium chlorate via isolation of solid ammonium chlorate.

[X-Wulf]

I'm seeing plenty of references to texts and articles from the 19th and early 20th century ... has anyone actually made this stuff in the last 92 or so years?

Surely the best way to truly determine the sensitivity of NCl3 would be to synthesise small (less than 5ml) batches and experiment with it. The synthesis reaction seems fairly straight forward (according to Mega's site), and the precursors are easy to come by. The only snag would be working with chlorine gas (this stuff was, afterall, used to kill people during the wars).

Small amounts such as this, whilst still packing quite a punch, shouldn't cause the loss of any limbs (as long as decent safety equipment is worn and safety principles adhered to). And experimentation would allow us to dispel any myths surrounding NCl3 (or verify its insane sensitivity).

[DeusExMachina]

I have only tried making AP a few times but was unsuccesful because of wrong ingredients that I had (I'm going to get the right materials for it today or tomorrow). I do not have a lot of experience with explosives but I know a lot about them and you shoud be very careful. It seems to me that the easier an explosive is to make, the more sensitive it is. If you really want to make nitrogen trichloride, make it in small amounts since as another member brought up the question "What do you want more - nitrogen trichloride or fingers?" The same with nitrogen triiodide, it can be set off by a feather so you should make it in small amounts. Even if an explosive is not very sensitive, you should start making it with small amounts and then when you know you can handle larger amounts, go for it.

[knowledgehungry]

:mad: Now wasnt that helpful :mad: . Of course it is safest to use small amounts first. Im sure everyone who deserves to keep their fingers knows that. ANFO is the easiest HE to make and perhaps the leastt sensitive.
Don't bother saying"I was just trying to help".

[DeusExMachina]

"Im sure everyone who deserves to keep their fingers knows that"

believe me, most people don't. There was nothing wrong with what I said. sure, it wasn't the most helpful thing but it was just a reminder. No need to be offended.

[kingspaz]

and no need to talk about how you some how managed to fuck up making AP when my dog can do it whilst balancing on its cock. try not to clutter the thread with useless crap. if you were speaking from experience then you have a right to warn. but like knowledgehungry said, anyone who doesn't know to make small amounts first deserves to lose there fingers. apart from the fact that anyone THAT dumb wouldn't be able to make it anyway.
it just seems a bit stupid when theres a guy who can't even manage to make AP dishing out advice about a much harder to synthesis explosive. no offence intended, i'm sure you will soon be able to make AP.

[DeusExMachina]

The only reason that it didn't work was because I was in a rush when I was getting my stuff. I picked up something a little different than acetone. Anyways, enough of this, it's getting off topic.

[Bo bo]

I have been thinking of making this explosive for quite some time, using welding flux as my source of NH4Cl but i'm not sure which ones contain this (don't you just hate it when products don't put the ingrediants list on?) anyone know a source of NH4Cl?
formula for my chosen method:
NH4CL+3Cl---&gt;NCl3+4HCl

[Anthony]

I'm pretty sure that NH4Cl is available as a dessicent in those little plastic dehumidifying boxes.

[frogfot]

Dessicant? But NH₄Cl isn't hygroscopic. I'm sure those "welding stones"(?) are pure NH₄Cl.
I tryed to run electrolysis of saturated solution of it for 1h with carbon rods, without any result. Solution just became yellow (probably from chlorine) and nothing have formed.. Though, because chlorine dissolved in liquid, big ammounts of NH₄Cl have precipitated.
Made a second try. I warmed solution during second electrolysis, to keep all salt dissolved. Got same results as above, yellow solution.. :confused:

I also have a book that have some info about Cl₃N, it got same method of preparation as you people say, prepared by leading chlorine through saturated solution of NH₄Cl. There was also some further info about conditions:
pH &lt; 4 yelds Cl₃N
pH 5-8 yelds NHCl₂
pH &gt; 8,5 yelds NH₂Cl - uncoulored oily liquid with strong smell

<small>[ December 14, 2002, 05:35 PM: Message edited by: frogfot ]</small>

[Marvin]

Electrolysis of a solution on its own is unlikley to work well, if you think about both the cathode and anode processes you would be producing 3 times the amount of base to 1 of NCl3 overall, not good news for a compound formed in strong acid solution. Eventually you lose enough N2 by reaction to make production possible, someone had some success using a current of 10-12 amps. Try adding a small amount of conc HCl first next time.

Ammonium sulphate is supposed to be slightly better than chloride when reacted with chlorine gas. I might be inclined to try chlorine from HCl/permanganate with ammonium sulphate, which is easier to get hold of anyway. Ammonium chloride will also form NCl3 when mixed with a sat solution of chlorine in sodium hydroxide (bleach is no use) and also a solution of bleaching powder. Ammonium chloride can be produced easily from the sulphate, for example by subliming it from a mixture with a chloride, or by mixing in aq soln with aq CaCl2 and filtering off with difficulty the CaSO4 produced.

In an experiment I have detailed here, a saturated solution of NH4Cl cooled in ice to around 0C, is added to an equal volume of a saturated solution of bleaching powder. After the reaction has subsided there is NCl3 both in a film/droplets on top of the solution, and at the bottom of the container. Addition of a drop of turpentine causes the top layer to detonate instantly, and the lower layer after a time. It can be distilled by leading a stream of warm air into the container and passing this through a receiver cooled in a freezing mixture. NCl3 evaporates fairly rapidly in normal air.

On the subject of the DIY-and-see-if-you-die method of assesing risk, whats important is not the 50 reliable reports of manufacture and detonation that make it safe, its the 5 reliable reports of it going off with no aparent external cause that make it unsafe. Reliable secondary sources are very important in this buisness as they alow you to assess the bulk of other peoples results. Put bluntly, understand the statistics, or risk ending up as one.

After reading a fair amount of info on NCl3 and the solid peroxides, I dont think anyone would be left with the opinion that they should be in the same risk catagory. This thread seems to have reached this conclusion allready, but I thought it useful to throw these points into the mix, particulaly as Ive just described another method of manufacture and that on its own this might be construed as an endorcement.

<small>[ December 14, 2002, 11:51 PM: Message edited by: Marvin ]</small>

[Pu239 Stuchtiger]

NH₄Cl is hygroscopic. I placed some in a tray to serve as an indicator of humidity; it is currently dissolved in the moisture it has absorbed from the atmosphere.

[X-Wulf]

Isn't cloudy ammonia (available in most stores for cleaning purposes) a solution of NH3 in HCl, thereby being NH4CL(aq)?

I agree with Marvin on the assessment of risk front. It's no good for those interested to simply produce and use NCl3 safely, we need to find out exactly what detonates it.
e.g. It may detonate on exposure to certain salts (such as urea - hence the reported detonation with the fingerprint), bases, oxides, extremes of temperature (or even light!), etc. There seems to be very little information regarding this aspect of NCl3, and that's the principle reason as to why it's so dangerous.

[spydamonkee]

hehe i can get bagfulls of ammonium chloride for "free"
not that i really wanna mess with nitrogen trichloride but im sure it has plenty of other uses in my field.
have not needed it y et but as the RTPB says something along the lines of "better to have and not need than need and not have"

I might just have to borrow a bagfull of it sometime... anyone know if it could be made into pure AN fairly simply?
CAN & Coldpacks are my only source of AN atm.

[metafractal]

X-Wulf, while what you say sounds right to me, I think that cloudy ammonia has such high levels of soaps, detergents, and other cleaning agents that it is effectiveley useless...
Edit: Sentance didn't make sense :p

<small>[ December 15, 2002, 07:15 AM: Message edited by: metafractal ]</small>

[Bo bo]

Found a source of NH4Cl under the name of Sal Ammoniac in an art and crafts catalogue, And even better for me 500gm of Aluminium powder. Check out art and crafts as a source of supplies, seem to have alot of useful items.

[VX]

Bo bo you can find ammonia solution in hardware shops in the UK. Not DIY shops like Focus, B&Q etc but the really old fashioned little privately owned shops. They are pure enough to work for making NI3, and ammonium chloride, so I assume they would work for other applications too, it's definitely worth a try anyway. Also try chemists for ammonia. The stuff I get is called 'household ammonia' and costs about 1 pound for about 500ml, it's not that concentrated, but it does work.

[Genital-Warfare]

Many people have made NI3 w/o incident; so, i would think NCl3 would be even more stable because of a higher electronegitivty, however i heard this is true, same goes with NBr3. Can anyione clear up why this happens?

CTR

[PEROMAN]

There is another method of NCl3 producing : from NaOCl , CH3COOH and NH4NO3(any ammonium salt)
The reaction is:
3NaOCl + 2CH3COOH + NH4NO3 = NaNO3 + 2CH3COONa + NCl3 + 3H2O
The reaction doesnt need any control - you just mix the solutions and wait 1-2hours , besides you dont need to work with gaseous chlourine A 5-7% NaOCl solution is used in Russia as a bleach
the method:(make it outdoors because of extremely bad smell!!!)
reactives :
300ml of 5-7% NaOCl solution ,
50ml of 70% CH3COOH
solution of 10gNH4NO3 in 30ml of water
1)cool the solutions in refredgerator (about -10C)
2) pour 300ml NaOCl into a 0.5l plastic bottle(cola)
3) add 25ml of CH3COOH to NaOCl by small parts
4) add the ammonium nitrate solution to the bottle by small parts(extremely bad smell ! the solution must become yellow)
5) add 25ml CH3COOH to the bottle by small parts
6) leave the bottle(dont close it !) for 1-2 hours The solution must become colourless and a yellow-orange liquid must gather on the bottom (about 10g)
Then close the bottle and throw it somewhere
(sorry for my english)

[PEROMAN]

I forgot something : Dont leave the bottle onder the sun !

[Mr Cool]

It doesn't look like acetic acid specifically is required for the reaction, so you could probably use an equivalent amount of any other organic/weak acid, such as citric, which is easier to find than 70% acetic acid. Just don't use vinegar, it'll give you a really diluted solution.
I'll have a go, it looks like an easy method.

[PEROMAN]

Of cource, any acid can be used .. Once i've made it with phosforic (but it is better to use weak acids) Also it is possible to use a mixture of acid and NH4NO3 solutions and to add it to hypochlorite
Does anyone know detonation rate of NCl3? Or just is it more or less then 5000?

[xyz]

Does it take a certain amount of time in the sun to go off or is it completely random?

PEROMAN, Are you able to throw the bottle without any problems? It seems a bit risky to me. If you are able to throw it though, I may carry out this synth using NH4NO3,NaClO, and HCl.

[PEROMAN]

NCl3 is not so extremely sensitive as some people say(most of them haven't ever seen it :D )
So throwing a bottle is quite possible (but of course , be carefull!!!)

About HCl :
I think it is not possible to use it
If you add HCl to hypochlorite - you would get Cl2 !!! Even if you add it drop by drop (i tried).
NaClO bleaches also contain NaCl , so , i chink , it's not possible to use any strong acid (such as H2SO4 and HNO3) because of reaction
NaOCl + NaCl + H2SO4 = Na2SO4 + Cl2 + H2O

But maybe , if you add the reagents in other ordinarity , you would get some NCl3(but with very low yield)

For example , if you first mix 1 mole NaOCl and 1 mole of NH4NO3 , you will get NH2Cl .Then, probably, if you add some HCl(and wait) ,you will obtain some NCl3 (maybe)
But i dont think it would work.

It's better to find acetic (any weak organic acid ) (maybe citric)
Or even phosforic(but the yield is low)

[xyz]

You want Cl2! The procedure takes NH4NO3 solution and the other two precursors (an acid and NaClO) are there solely for the purpose of forming chlorine gas. The Chlorine then reacts with the Ammonium Nitrate to form NCl3.

[PEROMAN]

The reaction between Cl2 and NH3(classical method) goes the following way :
1)Cl2 + H2O = HCl + HOCl
2)NH3 + HOCl = NH2Cl + H2O
3)NH2Cl + HOCl = NHCl2 + H2O
4)NHCl2 + HOCl = NCl3 + H2O
So , it's not necessary to obtain Cl2 , and then bubble it into NH4NO3
Besides, working with gaseous Cl2 has many problems.

[PEROMAN]

Maybe , using HCl is possible if wou add a mix of NH4NO3 and HCl solutions to NaClO (i'm not sure).
(or adding HCl to mix of NaOCl and NH4NO3 solutions)

[HyggeDK]

I have been reading this forum for some months now [I'm very impressed by the scientific and professional level of discussions in this forum], and thought it was time to make my first comment.

NCl3 has been in my thoughts for quite a few years, as it seems to be very powerful and very easy to make. However, I have never made it, because of the things I have read about it, like it will detonate if brought into contact with even traces of organic matter or if struck by sunlight.

Also, there has been an accident at a Danish university back in 1996 with this substance. A student was doing a synthesis involving chlorine and ammonium chloride in acidic solution. NCl3 was formed and the student, holding the beaker in his hand, lost one finger and one eye.

According to a German encyclopedia [Ullmann's, Band 9, p.386] the pH of the aqueous solution is determining the chloramine formed:

pH &gt; 8 NH2Cl is primarily formed
pH = 3-5 NHCl2 is primarily formed
pH &lt; 3 NCl3 is primarily formed

NCl3 is described as: Yellowish oil, Fp = -92C, Bp = 71C, pungent odor, extremely violent detonation even on gentle heating or shaking.

I once saw a webpage with chemistry demonstrations. One experiment was eletrolysis of an acidic solution of NH4Cl. Above the aqueous phase, there was placed an oil ["lamp oil" for lamps, garden torches and such]. So as soon as NCl3 was formed by the electrolysis in the aqueous phase, it would immediately rise to the boundary between the water and oil phase, react with the oil and create a spontaneous combustion in the oil/water boundary. Quite fascinating, and possibly a way to do a first-time preparation of NCl3 without too much danger. Unfortunately I didn't bookmark the page, and I don't remember the address.

One other thing that worries me, is the fact that the chloramines could also end up reacting further, forming hydrazine. So when experimenting with NCl3 it's probably a good idea to do it outside or in a fume hood [as almost all chemistry is done nowadays].

[frogfot]

Found a synth of NCl3 in nonorganic book where they let chlorine through solution of (NH4)2CO3 (9,6 g/30 ml water) (70% yield) or NH4Cl (0,5-1 g/5 ml water), while having nonpolar solvent above (as Hygge mentioned)
Used solvent is CCl4, CHCl3 or hexane. Though from previous many people here told that NCl3 decomposes/detonates in contact with organic materials?!

Deluted solutions is told to be safe to handle as long as conc does not go above 18%

[jeffchem2000]

Just a thought of mine,
If NCl3 is as friction sensitive or slightly less than NI3, and NCl3 is a liquid then there is a far higher chance of there being enough friction in the liquid moving to set it off. I have made NI3 and it was scary how easy it was to set off and so I would never want a liquid version of it.

[Marvin]

"One other thing that worries me, is the fact that the chloramines could also end up reacting further, forming hydrazine. "

HAhahahaha. Kind of 'be careful when making nitrogen trichlioride becuase you might form hydrazine'.

Roughly equivalent to a warning that the berylium reflector in a nuclear weapon might cause shrapnel.


NCl3 is mildy stable as a dilute solution in a fully chlorinated solvent, but I wouldnt use chloroform. Solutions in carbon tet are supposed to decompose slowly anyway with the production of phosgene, though this leads me to wonder where the oxygen comes from.

Nitrogen triiodide is more sensitive to shock when dry/ammonia deficiant becuase the ammonia adduct is actually a crosslinked polymer. This explains it breaking the general rule that liquids are usually more sensitive to shock.

NCl3 though is generally much more reactive, strong chlorinating agent and is much more likley to go off on contact with trace oils eg a fingerprint or as some demonstrations suggest, a drop of turpintine.

Yes, I am serious about the fingerprint. The risks are rather different and they dont belong in the same mental catagory.

[T_Pyro]

Nitrogen trichloride hydrolyses readily with water as:
NCl3 + 4H2O -> NH4OH +3HOCl
This property could be used to stabilise NCl3 to some extent, provided someone could come up with some way of promoting the forward reaction, and reversing it when required...

NCl3 was once upon a time used for bleaching food products, but its use declined rapidly when it was suspected that bread made from flour bleached in this way sent dogs mad! Well, if NCl3 could be used for bleaching, I'm sure there is a way to stabilise it, else I doubt it would heve been used in the first place.

Pierre Dulong discovered NCl3, and accidentally lost an eye in an explosion following his discovery. Just a warning to all who intend to make NCl3.

[Marvin]

Hydrolysis generally results in its destruction and keeping it out of contact with water would be a good idea, but all this is all rather acedemic as the liquid isnt stable enough to be useful. Theres a better way than making it, chemically converting it and remaking it from that. Its called making it in the first place only when you need it. Assuming you do want to make it though, and have no problems getting the chemicals or doing chemistry in a straightjacket.

For bleaching flour it was used as a vapour diluted by a large amount with air. I think someone said it was made electrolytically for this purpose and that this is detailed in a patent somewhere.

Dulong lost 3 fingers and an eye, though reports disagree somewhat as to if he lost them in the initial discovery, or during the long time he continued to experiment with it. Standard practice when this was acceptable, was to degrease all equipment with sodium hydroxide solution before use.

[Melvin]

Hallo,
I want to ask you some questions.You said that obtaining NCl3 was easy.I can tell you that I've used a less than a liter of HCl till tis moment to get the Cl2 gas and there is no NCl3.I made the solution with pH<4,4 ; I warmed the tube gently,not over 35C ,but there was nothing.
I want to obtain NCl3 by the reaction:

NH4Cl + 3Cl2-------> NCl3 + 4HCl
H+,t

I obtain the Cl2 gas by the reaction:

2KMnO4 + 16HCl ---> 2KCl + 2MnCl2 + 8H2O + 5Cl2

So do I have mistakes in the method.Can you tell me your experience!

[Marvin]

References in Mellor suggest that ammonium sulphate might be better than the chloride. They also say that if the chlorine is diluted with 1/3rd of air or CO2, no nitrogen trichloride forms, but not why. If your solution is not acid enough it will attempt to oxidise ammonia to nitrogen until it is.

You might like to try a variation, where a jar of chlorine is inverted in a conc solution of ammonium salt, and the liquid rises up as it absorbs chlorine and droplets of the oil fall to the bottom.

If you can get bleaching powder, that method might be easier being a tried and tested demo, if not you could also try saturating a 5% solution of sodium hydroxide with chlorine and mixing with a 10% solution of ammonium chloride. The ref doesnt give volumes for this sodium hypochlorite variation.

Wash all surfaces with dilute sodium hydroxide before use and keep fingers away from them. What concentration of ammonium chloride were you using, and what are the containers made of? Additionally the oil is very volatile so it could be be swept away by the gas stream.

Ive not tried any of this, I just have a fair amount of information.

[Myrol]

Is there a way to "stabilize" Nitrogentrichloride with a powdered Nitrate like pure Saltpetre (KNO3)? We can add some Fuel for more performance because the mix is Oxygenoverbalanced! Sulfur, Charcoal and Sugar are BAD because NCl3 could react and explode accidentely with the mix! Hint: NCl3 is not that tremendous unstable like often mentioned in this Thread but i know NCl3 is sensitive against bright sunlight :eek: and organic impurties! He is also only 24h useable what a shame!

[Mr Cool]

It can be rendered undetonatable by dissolving it in a solvent, but even then it is no more stable. You'll still get decomposition.
Mixing it with anything solid is just going to cause you problems.

"NCl3 is sensitive against bright sunlight :eek: and organic impurties! He is also only 24h useable what a shame!"

As you said, it's too unstable for any practical use as an explosive.

[Pthunder]

This is not to be taken lightly. I had an unknow amount blow up in my face an 8-19-04. It came as a by product of tri-chlor tabs used for water sanitizing. I could have been killed where I stood.
I am VERY lucky that things were ALL in my favor. If you should choose to mess around with this stuff best of luck and have good medical coverage because you will need it!
Here are some quotes:"Any conditions which allow NCL3 to form and collect as a liquid are extremely hazardous."
Vapor-"NCL3 vapors can be exploded or decompose (toN2 andCCL2) when concentrations in air are as low as 0.3%.....At concentrations of 3-4% the detonation is explosive with an instantaneous pressure rise."

[Myrol]

Like everybody here said: making NCl3 is just wasting time and perhaps loosing fingers etc. I hope you learned something due to this accident!

[Pthunder]

please re-read my post I never said that I was making it!! I said it was a by product of water sanitizing. Trichlor tabs to be exact. This was an industrial accident nothing more. I don't know where you got the idea I was trying to make this stuff intentionally!

[Melvin]

Hallo chemists!
I'm curious if someone of you have obtained NCl3! In the books it's written so much so I can say many things about it without obtaining NCl3.
So if anybody has obtained it let me know how did he does it?

[K9]

Someone (no this actually wasn't me :p ) told me that they mixed ammonium nitrate and calcium hypochlorite which proceeded to "snap, crackle, pop, and go bang". I'm assuming this was NCl3 that was formed because - 1. it can be formed in that reaction and 2. there was almost spontaneous ignition. That just goes to show you the danger of it.

[kddflx]

Hey, the reason it probably imediatly ignited is because the sodium hypochlorite will form sodium hydroxide, instead of water like with hypochloric acid. NCl3 is most stable in a acidic enviroment, not a basic one.

[Marvin]

Thats correct kddfix, but the reaction usually oxidises ammonium compounds to nitrogen until its acidic enough to form NCl3. This seems to be the case because it wont even form in alkaline enviroments and the reaction evolves a lot of gas.

NCl3 likes to off from contamination, trace oils, fingerprints. Difficult to point the finger at what caused the problem, but not as difficult as it would be for someone who plays regulally with this stuff.

[Bugger]

I thought that the "classic" or original method by which NCl3 was made in the 19th century was by reaction in the gas phase of NH3 with Cl2, catalysed by UV light (direct sunlight would probably do). Intermediate products are NH2Cl and NHCl2. The poor bastard who first made it soon blew himself up, and was severely injured. Not all the NH3 is likely to be converted, because some of the HCl byproduct would react with unreacted NH3 to form NH4Cl which is a solid.

Having been previously involved with water treatment, I am aware that NCl3 is a byproduct of water chlorination, along with NH2Cl and NHCl2, where NH3 is present as a decomposition product of proteins. Amines resulting from protein decomposition would also be chlorinated, but the organic part of them would probably be monochlorinated first.

I have heard of NI3, also explosive, being made by adding iodine bought OTC with ordinary household ammonia solution.

Bugger.

[Mr. Pseudo]

The 1% iodine tincture must first be boiled away, leaving a tiny amount of crystalline iodine. Simply using straight iodine tincture will result in nearly zero product, due to NI3's very slight solubility in water

(Are you sure the I2 won't sublime with the heating? - kingspaz)

[Marvin]

"catalysed by UV light (direct sunlight would probably do). "

No, and these are suitable conditions for an accident. Strong light can make the product explode.

NH3 + HClO <> NH2Cl + H2O is facile, as are subsiquent steps, so in acidic solution you get NCl3 formed together with a little nitrogen from side reactions and in alkaline solution it decomposes.

Successful production depends on using the salt of a strong acid in at least mild acid solution, or chlorinating for so long ammonium chloride forms.

"The poor bastard who first made it soon blew himself up, and was severely injured. "

As has been mentioned in this thread allready. Pierre Dulong, 2 or 3 fingers and an eye.

"I have heard of NI3, also explosive"

If it isnt on the forum allready it must be very rare, perhaps you should start a thread about it.

[jimmyboy]

In a dream i decided to try mixing calcium hypochlorite and ammonium sulfate in a small disposable dish - i then proceeded to put a few ml's of 30% HCl on the mixture - it bubbled and fumed of chlorine and water vapor - the mixture was a creamy greenish tint and finally stopped bubbling - any ideas? will the sulfate ion destroy the reaction?

[Bugger]

No, the sulfate ion will not destroy the reaction, because it will react with the Ca++ present to form a precipitate of sparingly soluble CaSO4, which may have caused the opacity you saw. The hypochlorite would be free to react with the NH4+, resulting in more Cl-, which would be hastened by acidification, so NCl3 and partially chlorinated NH3 and NH4+ are likely.

Bugger.

[jimmyboy]

In my dream i still felt that calcium hypochlorite's insolubility was interfering - the interaction of ph, chloramines, ammonia and trichloride seems to be a fairly complex reaction - i decided to replace sodium hypochlorite in its stead and the reaction proceeded much the same bubbling with water and chlorine vapor - then it was left to subside and sit there for a few hours - nothing so far - i guess i will give up on this reaction for now - was just looking for a few simple snaps with a small amount of reactants to see if there was any weight to these equations - it may be that i need much more concentrated starting materials for this to proceed - i will try again some other time

[Mr. Pseudo]

Wow...When posting that last thread, I recalled making about 20g of NI3 and never using it. I did a thorough search of my lab, and finally found it in a small vial hiding behing the glacial Acetic acid. I had the crystals washed and stored under ether, but now there is simply an opaque black solution with no settled particulate matter. I'm wondering if the crystaly simply fell apart over time and released trapped iodine. There also seems to be a thin translucent brown layer on top. A quick spin in the 'fuge woud reveal and crystals, but that is certain to cause nasty repricussions.

This stuff is literally 2 years old, and it is some freak of memory I actually remembered it. What I think probably happened, was that the unstable NI3 slowly broke down over time, releasine Iodine into the ether. The large volume of N2 produced could have escaped over such a long period, and there also appears to be some degree of solvent loss, and I2 discoloration on the wax seal.

I was going to ask if anyone had any ideas about how this could have happened, but I think I answered my own question.

BTW - sorry about the k3wl moment kingspaz, i've gotta stop posting so late.

* X-P

[A.Scriabin]

Hi! I've made some NCL3 few days ago mixing NaClO(5%),NH4NO3 and later HCl in order to produce Cl2 gas and reduce pH. It's very important to make this procedure in the dark. At the beginning the mixture becomes light green with a lot of effervescence. After about 20-30 min, the mixture turns clear and you can see several bubbles green-yellow on the bottom of the beaker, (as the same way CHCl3 in the water). This is NCl3, but it very very difficult to separate becouse it has incredible smell that starting to burn your eyes if you get closer. Even if you succeed to separate NCl3, it fades after few minutes in presence of light. I've tried to burn a very small amount, it deflagrates by burning the surface on it leans.

Sorry about my bad english(I'm italian <_< )

[Bluebottle]

"I've tried to burn a very small amount, it deflagrates by burning the surface on it leans." Please clarify this.

Are there any possible uses for NCl3 as a reagent? I heard somewhere of the solution in CCl4 as nonexplosive (yet still rather unstable). For example to introduce N or as a chlorinating agent?

[A.Scriabin]

I've put NCl3 on a plastic pen..after the deflagration(a yellow flame),the pen was burned seriously where before was NCl3. Without NCl3,burning the same pen is difficult.

[Bluebottle]

Excuse me, but that doesn't quite seem right... How much NCl3 was this, and furthermore, you are certain that this was in fact NCl3 and not mono- or di-chloramine?

[chemist646]

I perform the NH3 and HCl method, it find it much easier.