Sciencemadness Discussion Board - Trichloride failure

Trichloride failure

Tdep - 9-7-2013 at 20:07

Hey guys

Been attempting to synth some nitrogen trichloride.
I know, I know, danger. But I've been unsuccessful.

I mixed ammonia and conc. HCl to make NH4CL with a slight excess of HCl. Then added 4% NaOCl untill the entire solution went lemon yellow (this was conducted with full protection in an ice bath). However, no oily trichloride droplets seperated out.

Any changes you could suggest to what i'm doing in order to be successful?

Thanks.

chemcam - 9-7-2013 at 20:19

IIRC bubbling chlorine gas through a warm solution of ammonium nitrate will work. I have never done it nor do I remember who told me but its written in my notes to look into.

Nitrogen trichloride is very sensitive to pretty much everything. I hope you know what you're doing, it seems you might not though so be careful. Please.

Tdep - 9-7-2013 at 20:40

Treating everything I mix as dry NI3 don't worry.

I did try that once, didn't work for me and since then my ammonium nitrate has become to valuable to use on something that doesn't need the nitrate ion.

My current system should work though?

chemcam - 9-7-2013 at 20:44

Im not sure about your method never heard anything about it, when you used the ammonium nitrate solution did you heat it?

Tdep - 9-7-2013 at 20:58

I didn't, that's probably a notable point. I might try it again, IIRC I kept it at icebath temperatures

I got it from the bottom of this thread http://www.sciencemadness.org/talk/viewthread.php?tid=2079

[Edited on 10-7-2013 by Tdep]

AndersHoveland - 9-7-2013 at 21:56

The pH has to be within a certain range, if it is too low or too high, nitrogen trichloride will not be able to form.
The optimal salt to use is ammonium sulfate (having to do with the pH), and then pass in chlorine gas.

http://books.google.com/books?id=QQkSAAAAIAAJ&pg=PA2178&...

Be sure to wear protective safety goggles! If the oily droplets start forming on the bottom of the glass detonate (which they are likely to do for no reason), even a very small amount could shatter the glass and send fragments into your eyes.

Another strategy is to have a layer of chloroform which the NCl3 can go into as it forms. NCl3 dissolved in excess chloroform is supposedly relatively safe to handle.

Likely reactions, if you were wondering about the chemistry of nitrogen trichloride:

NCl3 + HNO3(aq) + 3 H2O --> NH4NO3 + 3 HOCl

NCl3 + 4 HCl(aq) --> NH4Cl + 3 Cl2

NCl3 + 2 NaOH --> 2 NaOCl + NH2Cl

NCl3 + 2 NH3(aq) --> 3 NH2Cl --> further decomposition

Quote: Originally posted by Tdep

Any changes you could suggest to what i'm doing in order to be successful?

Chlorine does not really oxidize ammonium ions. There is, however, a small equilibrium. If you want some NCl3 to form, the NH4Cl should be very dilute.

The reason why passing chlorine gas into ammonia does not work is because chloramine initially forms, and it is not stable for long in ammonia or alkaline solutions.

[Edited on 10-7-2013 by AndersHoveland]

chemcam - 9-7-2013 at 22:08

That chloroform bit is interesting, have you done it personally?

Thanks for those equations as well. Nice to see them together in one place.

Tdep - 9-7-2013 at 22:09

That seems a likely explanation. I believe it may have been too acidic then after the addition of the bleach, too basic.

I'll give it a shot another day with the passing chlorine through a warm solution of ammonia sulphate. That seems like a good idea (as far as NCl3 goes I guess )

I built a little bunker for the apparatus in my backyard, partly because shrapnel and partly to keep it in the dark (as I read somewhere about detonation of it on exposure to sunlight; scary stuff!). Of course I wanted it outside due to the wonderful mix of gases you get when you violate every warning or every bit of packaging and mix bleach, ammonia and hydochloric acid.

Tdep - 9-7-2013 at 22:21

Chemcam, would love to see some of this stuff in action on your channel. You wouldn't be one to shy away from a challenge would you?

chemcam - 9-7-2013 at 22:49

Challenge accepted. I take requests all the time and try to do most of them in a timely fashion just that the recent holiday took all my time as you can see by the show I put on. Which by the way, I was hoping to earn a unique title dealing with pyrotechnics... 'professional pyro' would have been nice.
But anyway yes I will make a video about this. Is there a certain way you want it done or just do it my way?

[Edited on 7-10-2013 by chemcam]

woelen - 9-7-2013 at 23:04

Another way to make NCl3 is electrolysis of a solution of NH4Cl using a graphite anode. At the anode, Cl2 is formed, which reacts with the ammonium ions to NCl3. The NCl3 tends to move upwards, together with the bubbles of chlorine. In this way, you can do the experiment relatively safely, because with electrolysis for just a few minutes you get very small amounts of chemicals.

I read that if you have a layer of unsaturated hydrocarbons (e.g. hexene) or turpentines on the solution of NH4Cl, then the bubbles of chlorine, which have NCl3 with them in the form of small droplets lead to small flashes of light when they mix with the organic layer. The NCl3 then reacts violently with the organic and this triggers an explosion of the small droplet. I never tried this myself though.

Tdep - 9-7-2013 at 23:08

Would talking be too much to ask for?

Ammonia sulphate appears to be the way to go, so a few shots of your set up would be nice. Not asking for a tutorial (hate to see very inexperienced people try it!!) but just the real practical logistics that go behind this chemical such as how to cope without plastic, how to cope with possible shrapnel, excess chlorine is rather interesting.

Unless you try another way and we can compare results? I plan to post a video on this, once I've got it working of course.

Also, don't die.

chemcam - 9-7-2013 at 23:12

Alright I think what I will do for the video is a collaboration of all these mentioned ways to do it, electrolysis included with even this violent reaction with an organic layer. I don't have hexene but possibly some old unknown purity turpentine that I shouldn't use probably. What else could work?

I am going to bed now so in the morning I'll catch up on this thread and get started experimenting for the video. If somebody wants to organize the different methods into a list for me that would greatly help and I will give credit in the video to your channel or website or whatever is needed.

I talk in the videos lol just not certain ones, people always give me shit because I sound like a city slicker and not a nerd, but, I will do the video well and narrate entirely.

I am very cautious though, so don't worry. If I die I'll make sure beforehand I tell someone to log on here and explain what happened to me so the same mistake is avoided.

[Edited on 7-10-2013 by chemcam]

AndersHoveland - 9-7-2013 at 23:27

This is a little topic, but we all know that hydrazine can be made from hypochlorite and ammonia. Some sources get more specific and state it is the chloramine attacking the ammonia. No doubt this will not seem like any big mystery to most of you. After all, hypochlorite is an oxidizer. However, when one starts examining the chemistry of hypochlorite and ammonia in other situations, one realizes that hypochlorite would not be able to oxidize NH3 like this, at least not directly. So it really becomes a sort of mystery, the exact reaction mechanism.

I have a hypothesis about how NH2Cl can oxidize NH3. The reason the reaction is so facile is likely because the hydrogen being oxidized never comes off the nitrogen! The two reactants combine to form hydrazine chloride. None of the hydrogen-nitrogen bonds break, and the nitrogen-chlorine bond is quite weak to begin with.

Of course, under normal conditions, the hydrazine gets further oxidized (to N2) much faster than it forms. The reason N2H4 is such a reactive reducing agent is that the nitrogen atoms contain lone pairs that are very repulsive. N2H4 is much less stable than either NH3 or N2 because not only is the nitrogen atom closely bonded to three other atoms, but one of those atoms also happens to be another nitrogen atom.

It is commonly stated that the NΞN triple bond is incredibly strong, but I believe that is somewhat inaccurate. The more likely reason the formation of N2 releases so much energy is that the nitrogen atoms are more stable bonded to just one other atom so long as their valence can still be satisfied.

In the case of NCl3, it would likely not react the same way as NH2Cl with NH3. In the case of NCl3, the nitrogen atom is more electronegative than any one of the chlorine atoms, therefore it hydrolyzes to NH₄⁺ ions and HOCl, rather than HNO2 and HCl. No doubt part of the reason the central nitrogen atom is so electronegative has to do with the other two chlorine atoms it is bonded to (I am sure they are very electron withdrawing), which alters its electronegativity.

In contrast, with NH2Cl, the chlorine atom is more electronegative than the amino group, so it is the chlorine atom that acts as the electron acceptor. The only reason the NH2Cl can hydrolyze to ammonium ions is because it can get protonated, thus changing the electronegativity of the central nitrogen atom. Thus, I think NH2Cl could react either way, probably depending on reaction conditions.

[Edited on 10-7-2013 by AndersHoveland]

Tdep - 10-7-2013 at 00:07

Well there's the electrolysis, the bubbling chlorine through an ammonia salt (or a set up more like the one here http://www.lateralscience.co.uk/oil/)

Then, I saw a while back, I have no idea if this is complete BS or not, that it can form on kids pants after they pee in the pool as the urea reacts with the hypochlorite in the swimming pool.
To me, that's completely morbidly hilarious.
If you feel like putting your myth buster hat on i'd love to see this confirmed or denied.

AndersHoveland - 10-7-2013 at 00:29

Yes indeed. One time the door was left open to a little room under the big pool at my university. I went inside and there were two chlorine generators, each a little bigger than a washing machine. They both had lids, and apparently they worked by adding hydrochloric acid and calcium hypochlorite pellets. There were several big plastic barrels and buckets of these chemicals in the room. There was a big warning sign on the lids warning not to use Triklor (TTCA), that it would cause an explosion.

I read on some other site a pool treatment expert wrote that "The oxidation of ammonia by chlorine produces about 90 % nitrogen and about 10 % nitrate." Not sure if this is true, and if so it could just be a UV catalyzed reaction, being exposed to the sun all day.

Quote: Originally posted by chemcam

Are you proposing this as an experiment for me to add in the video? If so I would need more details

not sure what you mean, but if you want to make chloramine gas, it is fairly simple. just mix ammonia and bleach. I am sure much of the gas that comes out is also nitrogen, chloramine is not very chemically stable.

be warned, the reaction can be can be violent with solid hypochlorite, and chloramine gas is poisonous.

[Edited on 10-7-2013 by AndersHoveland]

woelen - 10-7-2013 at 01:57

Quote: Originally posted by Tdep

Well there's the electrolysis, the bubbling chlorine through an ammonia salt (or a set up more like the one here http://www.lateralscience.co.uk/oil/)

This describes an insanely dangerous experiment. Do NOT repeat this. You should use electrolysis for just a few minutes, because that produces the NCl3 in small amounts and no big blobs of oil are collected!

Quote:

Then, I saw a while back, I have no idea if this is complete BS or not, that it can form on kids pants after they pee in the pool as the urea reacts with the hypochlorite in the swimming pool.
To me, that's completely morbidly hilarious.
If you feel like putting your myth buster hat on i'd love to see this confirmed or denied.

This must be complete bullshit. Urea and hypochlorite do not react to form NCl3. They can react with formation of NH2Cl, but most of it reacts to N2. Further, any pee would be highly diluted and the hypochlorite also is highly diluted in the swimming pool. Visible reactions of this type require at least household bleach, without dilution!

plante1999 - 10-7-2013 at 03:48

I think I have done a video about this a while ago. About nitrogen trichloride solution, one might be able to find it on youtube...

Tdep - 10-7-2013 at 05:36

Oh yeah, yours is the only video there showing the chemical.
It's interesting, if a tad slow but slighty disappointed you didn't show any of its properties.

I mean, compared to the number of NI3 videos on youtube there is only one showing NCl3. I think such an interesting compound deserves a few more (even if it is evil).

plante1999 - 10-7-2013 at 05:49

It was a while back, and I had hard time speaking English t that time, I wasn't very good at editing video, and my computer was/is way too slow to properly edit them, that's why I stopped making videos.

The compound in solution slowly decompose to chlorine and nitrogen, it can dissolve various metal, and that is pretty much all what I have tested.

Tdep - 10-7-2013 at 05:56

Don't worry, i've made muchh worse videos than that in the past. It's still very interesting and unique atm, which is hard to come by on the youtubes now.

Is there any use for that solution of it in chloroform? Or just an interesting compound to make?

Also, I know it reacts with plastic, but here's a question: What about PTFE? Surely NCl3 wont oxidise that?

chemcam - 10-7-2013 at 08:02

Quote: Originally posted by Tdep

Well there's the electrolysis, the bubbling chlorine through an ammonia salt (or a set up more like the one here http://www.lateralscience.co.uk/oil/)

The title from the link really puts it in to perspective "fearless scientists with missing body parts"
I should build a robot to do this for me, maybe for now I will just bubble chlorine into an ammonium salt, since that is what I am comfortable with.

While I have the NCl3 I was thinking about this:
NCl3 + 3KBr = NBr3 + 3KCl would it work with NaBr instead of KBr?

Plante, I didn't know you had a NCl3 video, I just watched it, good job.

EDIT-
I would love to pee into a beaker of 8% bleach and I'll also find the minimum amount of urea to visibly react with that 8% bleach. (separate video though)

[Edited on 7-10-2013 by chemcam]

bfesser - 10-7-2013 at 11:00

<a href="http://www.lateralscience.co.uk/oil/" target="_blank">

Quote:

<center><strong>A horrific accident in 1866 illustrates the power and sensitivity of nitroglycerine.</strong></center>…
"In the auction room of Cobb and Sinton, on the east side of Montgomery Street, a human brain, almost intact, and other fragments of the body near it, were found. A piece of human vertebrae was blown over the buildings on the east side of Montgomery Street, where it was picked up in front of Squarza's, on Leidsdorff street. A piece of skull was lying on California Street, east of Leidsdorff, with other fragments of human remains, and a human arm struck the third story window of the building across the street." <img src="../scipics/_ext.png" />

</a>

AndersHoveland - 10-7-2013 at 11:51

Nitrogen trichloride is much more sensitive than nitroglycerin!

Nitrogen trichloride frequently explodes for no reason while it is being formed. It is so sensitive, that the detonation of a single tiny drop is typically enough to propagate through the water and cause simultaneous explosion of all the other oily drops in the reaction container. I read somewhere that even a tiny little spec of organic dust falling onto a drop of this oily liquid can trigger detonation.

There is absolutely no way that one could even collect a test tube of this stuff, much less store NCl3 in its pure state. If you are preparing NCl3, you need to assume that it could explode at any moment, and handle it appropriately.

Another thing to possibly consider here is that NCl3 is supposedly a neurotoxin, so probably not a good idea to have any skin contact.

[Edited on 10-7-2013 by AndersHoveland]

chemcam - 10-7-2013 at 11:56

I was thinking of doing it with the chloroform layer like plante did in his video. Would that make it quite a bit safer or is that a myth?

AndersHoveland - 10-7-2013 at 12:01

Quote: Originally posted by chemcam

I was thinking of doing it with the chloroform layer like plante did in his video. Would that make it quite a bit safer or is that a myth?

It can not explode if it is diluted enough with chloroform. Still, one should use caution.

Tdep - 10-7-2013 at 19:19

Quote: Originally posted by woelen

This describes an insanely dangerous experiment. Do NOT repeat this.

Hey Woelen.
Just so I cover all bases in designing my set up, can you list me a few reasons why that site's set up is so horribly wrong as apposed to a chlorine bubbler?

Is it just the amount it creates? Obviously I have no intentions of moving or storing the substance (as in Meglomania's case, sucking it up with a medicine dropper. Not trying that...)

Or are you saying electrolysis is the only way? Is electrolysis considered safer (maybe 'less dangerous' is a better term here?) because you can easily control the scale of the trichloride? Or is it more to do with the formation of smaller blobs of the chemical as apposed to one large mass?

I hope my speculation hasn't gone too far and I don't come across as a real idiot. I'm glad you let us discuss such a dangerous experiment and I'm thankful for the help with keeping safe.

AndersHoveland - 10-7-2013 at 21:56

Just keep the amounts small, do not have more than tiny amounts in one place. I would not suggest making any more than a milliliter, if you do not plan to have it dissolved in chloroform.

Use a plastic tray or something to catch the reaction solution if the NCl3 drops on the bottom detonate and the glass container shatters, which would cause a spill. In fact, you might want to consider using a plastic cup for the reaction (I do not know if this might interfere with the reaction, though)

It would probably be a good idea to wear thick rubber gloves a thick long sleeve clothing, to help stop the glass shrapnel if there is an accident. I also suggest you keep a small distance (6-12cm) between your hands and the NCl3 at all times. Even a small amount of distance can make a big difference if something goes wrong.
ALWAYS wear protective plastic eye goggles.

NCl3 most often explodes as it is being formed. If you have some crazy idea that you can fill a little test tube with it, you obviously are not understanding the meaning of this post. NCl3 is touch sensitive, it is a very unstable compound !

[Edited on 11-7-2013 by AndersHoveland]

Variscite - 10-7-2013 at 22:43

This stuff sounds way too dangerous for me to even think about synthing it. Seems like an interesting compound though, like NI3's less popular brother. Maybe some day...

Tdep - 10-7-2013 at 22:54

Good advice! Except

Quote: Originally posted by AndersHoveland

In fact, you might want to consider using a plastic cup for the reaction (I do not know if this might interfere with the reaction, though)

It's the common sense thing to do but NCl3 is destroyed on contact with plastic.

One safety feature idea is having all the glass is in a huge plastic tray so if (when?) the glass shatters any undetonated NCl3 would hit the plastic and be destroyed.

However, a sizable blob of it is most likely going to have a violent reaction with the plastic, which means even more explosions. So maybe it's not a good idea...

But yes. Explosion at any time, even when just forming. Like hell am I using any real expensive glassware for this haha

AndersHoveland - 31-8-2013 at 08:32

found this:

Quote:

Hydrazoic acid is also made by treating nitrogen chloride, NCl₃, or an aqueous solution of silver nitrite with hydrazine sulfate.
With sodium hypochlorite and acetic acid, hydrazoic acid furnishes a colourless highly explosive compound, N₃Cl.

“Modern Inoraganic Chemistry”, J.W. Mellor, (1912) p551,552

The entry discussed the chemistry of HN3, but happened to mention NCl3. So apparently NCl3 can be reacted with hydrazine to form some HN3, and also the reaction between HOCl and HN3 is analogous to that between HOCl and NH3 when it is forming NCl3, interesting from a chemical perspective.

Obviously, due to the unstable nature of NCl3, these reactions were probably done in a very small scale, and may not be a practical way to prepare HN3.

[Edited on 31-8-2013 by AndersHoveland]