Sciencemadness Discussion Board

Ammonium chlorate?

lucky123 - 29-6-2008 at 15:36

I read online that electrolysis of ammonium chloride to try and make an ammonium chlorate or perchlorate is a not something to try because of dangerous explosive materias that will form? My question is what forms when this is done???

JohnWW - 29-6-2008 at 15:43

Chloramines and NCl3 are likely to be formed.

chlormines and nacl3?

lucky123 - 29-6-2008 at 16:30

What is Nacl3 and chlormines where can I find a link with info about them and how dangerous are they... More dangerous them the peroxides?

not_important - 29-6-2008 at 16:43

Quote:
Originally posted by lucky123
What is Nacl3 and chlormines where can I find a link with info about them and how dangerous are they... More dangerous them the peroxides?


uh - do a Web search?

The discoverer of nitrogen trichloride lost an eye and several fingers in explosions caused by NCl3. Some old chemistry books have a demonstrative preparation using electrolysis of NH4Cl; done outside with a film of turpentine on top of the solution, the 1st drop of NCl3 to reach the surface causes an explosion, usually destroying the equipment.

Formatik - 29-6-2008 at 17:05

NCl3 is much more dangerous than some organic peroxides (MEKP, cTATP, HMTD), because it is much more reactive, and probably close in power.

Ammonium chlorate itself is also very dangerous as it tends to explode spontaneously because of the its decomposition products like free HClO3 and ClO2.

IrC - 2-7-2008 at 17:46

NCl3 is much like the iodine cousin, so sensitive (especially NI3 when it dries) that a fly landing or a sudden breeze sets it off. Notice I did not say CAN set it off, rather WILL set it off. These chemicals should only be made in very small amounts and good luck ever storing any. I love making this stuff for fun when bored but the one time I ever made it in quantity completely cleared all glassware off of a large bench which had several other experiments going on at the time, making a mess which kept on giving all day. By this I mean not only did the floor and various and sundry furniture keep popping loudly for the entire day, but so did I. After 20 minutes or so of this in study hall I was asked to go outside until my clothes stopped exploding. I should mention that 3 seconds after the initial big bang I was completely soaking wet. I was making this in a 1000 mL beaker which was full to the top. I was actually watching this when it exploded, lucky me my teacher was a stickler about face protection or I would have had eyes nose and mouth full of ammonia. This was in 1969, so I shudder to think about the number of years I would have lived as a blind person.

The class was mid day, study hall was 2 hours later, where I was still popping loudly constantly, and at the end of the day as I was walking home I was still going off every minute or two. Each little bang left a violet stain which by the end of the day had ruined both my shirt and jeans (we didn't know about tie dyeing then otherwise I may have been improving my look as time went on). I do remember my mom being pissed but not nearly as much as the principle was.

He tried running me through the ringer for blowing up one of his classrooms, but my science teacher was cool, covering my ass and convincing everyone it was an accident which could not have been avoided due to tainted chemicals. Of course both He and I knew this was pure invention. Later He did bitch at me for scaling up the formula. He always said he did not care what mad science I did as long as he first saw the complete plan including all amounts of all chemicals. I had taken my formula and scaled it something like 15 times from what I showed him when getting his permission. Good thing he was on my side as later I heard over a grand worth of school property had been wasted!

How to make NCl3

bigbigbeaker - 2-7-2008 at 19:36

See http://www.sas.org/E-Bulletin/2003-05-16/chem/body.html
The writeup by Norm Stanley gives a prep that works nicely.
I took old D cell batteries apart for the carbon electrodes. Norm says" There is, however, a way to safely demonstrate the instability of this compound. Prepare a saturated solution of ammonium chloride in water and warm with a hot plate or low Bunsen flame. Float a thin layer of turpentine on the surface and insert carbon electrodes (Figure 2). Apply a low DC voltage (ca. 6 V) from a lantern battery or suitable power supply to electrolyze the NH4Cl. Hydrogen and ammonia are evolved at the cathode while chlorine is evolved at the anode. Minute droplets of NCl3 are formed at the anode in accordance with equation 8. These will rise and decompose on contact with the turpentine giving rise to a crackling sound, a flash of light and a puff of white smoke as each droplet explodes. Some experimentation with the conditions of electrolysis may be required to exhibit all these effects; When I tried this experiment (a long time ago) I saw only the smoke."

Formatik - 12-8-2008 at 14:45

Quote:
Originally posted by IrC
NCl3 is much like the iodine cousin, so sensitive (especially NI3 when it dries) that a fly landing or a sudden breeze sets it off. Notice I did not say CAN set it off, rather WILL set it off. These chemicals should only be made in very small amounts and good luck ever storing any. ...


According to Gmelin, NCl3 doesn't seem to be shock sensitive citing a reference (W.T. Chamberlain, Jber. 1888, 2723) where it was filled into grenades without premature explosion, that's wrong though because NCl3 detonates under a hammer blow, but it can be suctioned with a clean dropper so it is nothing as sensitive as NI3. It used to also be produced in large kilogram amounts on the industrial scale. But the main risk is it's high reactivity. NCl3 explodes extraordinarily easy when irradiated with sunlight or diffused day light, very violently from magnesium light. Magnesium light gets the strongest, and red light the weakest explosion. The temperature of explosion varies with some references giving, 60 or 71 deg.C.

It will detonate on contact with many compounds and materials, fat say from fingers on glassware is enough to detonate it. My previous assumption that it approaches the power of some organic peroxides was based on the literature descriptions of its violent detonations and an VOD estimate of 4700 m/s at 1.6 g/cc which was similar to that known of another nitride, S4N4, which is 5190 m/s at 1.6g/cc, using a method meant for CHNO compounds. According to Gmelin the heat of explosion of NCl3 is 316 cal/g, its brisance is said to be a bit lower than regular black powder (R. Wagner, C. 1872, 125). But if black powder exploded this readily it would also be known for its violence. I doubt this though because NCl3 can detonate nitrocellulose.

It usually detonates violently on contact with organic materials like fats and volatile oils - chlorinating them, fats such as palm oil, train oil, linseed oil, myrrh, pig fat, which is why containers containing the compound beforehand must be carefully defatted. The same is with pavements and soaps, whereas with K-, Mg-, Ca-, and Ba- soaps there is only strong effervesence. A droplet detonates on contact with olive oil, despite being under water, a tiny droplet under several mL H2O detonates "on contact" with turpentine (added to form a suspension). More on reactivity and solutions is in Gmelin. As to its formation, it can be simple to prepare from NH4 salts without electrolysis, like mentioned in another thread on this forum.

IrC - 12-8-2008 at 19:34

"NCl3 explodes extraordinarily easy when irradiated with sunlight or diffused day light"

Likely this is why I got the warning from my teacher many years ago. I cannot think of a reason to sit in front of a batch of this being made while sitting in a dark room. Usually sane people make this outside, likely in daylight. So it stands to reason why I was warned about making this one. Also, it is much more powerful than the iodide. This combined with the extreme sensitivity on the I3 means a much smaller amount of the I3 is made when it decides to go off for no apparent reason. Could you imagine the Cl3 accumulating into Kg amounts before it went off?

If anything, the I3 explodes faster than you can prepare huge amounts making it a relatively safer synthesis?

I forgot to add: the idea of storing NI3 under alcohol keeping it wet all the time for safety is also crap. I know, been there, done that. My chem teacher went over my data after my at home larger amount went off (a few weeks after the story where I wrecked the school lab gear). He surmised that possibly a large crystal started growing, and when large enough the inside of the crystal was dry enough to explode with no warning, or reason that I could find. I do not know if this was true but it seemed likely enough to be possible. He also said this was what caused my at school disaster, not sure if correct but again it sounded plausible.

[Edited on 8-12-2008 by IrC]

Formatik - 17-8-2008 at 20:44

Quote:
Originally posted by IrC Also, it is much more powerful than the iodide.


That's right, NI3 also can't detonate nitrocellulose: 6.5 g of NI3 (the mixture of ammoniate, etc) could not bring guncotton to explosion but 0.3 g Hg(ONC)2 could, with NCl3 it needed 3.25 g as mentioned in: Handbuch der angewandten physikalischen Chemie in Einzeldarstellungen by Georg Bredig, Wilhelm Bachmann, pg. 19 (1908), Vol. 9-10.
Quote:
This combined with the extreme sensitivity on the I3 means a much smaller amount of the I3 is made when it decides to go off for no apparent reason. Could you imagine the Cl3 accumulating into Kg amounts before it went off?


NCl3 is a pretty powerful tear gas (but not as harmful to the lungs as Cl2), so it would be even difficult to accumulate a large amount besides by remote controls in the industrial scale.
Quote:
If anything, the I3 explodes faster than you can prepare huge amounts making it a relatively safer synthesis?


Because NI3 explodes when scraped, and bumped under water with a rod, I'm sure there is likley a point where it just explodes. NI3 could be safer because it doesn't detonate as violently as NCl3. It's also not well known for injuring chemists.
Quote:
I forgot to add: the idea of storing NI3 under alcohol keeping it wet all the time for safety is also crap. I know, been there, done that. My chem teacher went over my data after my at home larger amount went off (a few weeks after the story where I wrecked the school lab gear). He surmised that possibly a large crystal started growing, and when large enough the inside of the crystal was dry enough to explode with no warning, or reason that I could find. I do not know if this was true but it seemed likely enough to be possible. He also said this was what caused my at school disaster, not sure if correct but again it sounded plausible.


What happened is typical of large crystals with highly sensitive compounds. The well known lead and silver azide suspended under water that if they form large crystals and then if internal crystalline stress is enough, they will detonate "spontaneously" (crystal breakage), this is also why Pb(N3)2 is dextrinated to keep aggregates small. Then if we consider a compound like NI3, which is much, much more sensitive than those azides, it's not hard to see the same happening with this nitride.

[Edited on 17-8-2008 by Schockwave]