Sciencemadness Discussion Board - Chlorinating agent thread

Chlorinating agent thread

plante1999 - 29-4-2011 at 16:09

You probably know that i made a uge amount of post about chlorinating agent , so i made a post for this.

First this post is for :
Report experiment
Synthesis chlorinating agent
Present chlorinating agent

So i will start the post.
I failed attemps to made Cl2 sol. in CHCl3 because it seam to react to form CCl4 in about 10minute or so.

I have read in a book that 15% sol. of NCl3 in CHCl3 is a very good chlorinating agent because the stability of Nitrogen and oxidizing proprety of chlorine. I want to attemp to made this but i want to know how synthethis it safely.

A way that ive readed:

sat. sol. of NH4NO3 witch have a botom layer of CHCl3. chlorine gas is passed through the chloroform so when it form the NCl3 disolve in the solvent.

Thanks!!

[Edited on 30-4-2011 by plante1999]

[Edited on 30-4-2011 by plante1999]

hissingnoise - 30-4-2011 at 04:48

NCl<sub>3</sub> can detonate if you look at it sideways . . .
An accident waiting to happen!

plante1999 - 30-4-2011 at 05:05

In fact in the book it said that 15% sol. is safe but at about 22% it become dangerous.

[Edited on 30-4-2011 by plante1999]

hissingnoise - 30-4-2011 at 06:01

Eyes and fingers are soooo irreplaceable!
I'd avoid that compound whatever your book says . . .

plante1999 - 30-4-2011 at 16:15

almost the same thing as my reference but online.

Attachment: NCl3.pdf (69kB)
This file has been downloaded 576 times

ScienceSquirrel - 1-5-2011 at 12:05

I would not consider using this as chlorinating agent unless there was a reaction that would not work with anything else.

plante1999 - 1-5-2011 at 14:14

Here my review of the brauer NCl3 sol. synthesis with somme changes.

<iframe sandbox width="425" height="349" src="http://www.youtube.com/embed/_IepxokbayQ" frameborder="0" allowfullscreen></iframe>

[Edited on 1-5-2011 by plante1999]

[Edited on 1-5-2011 by plante1999]

[Edited on 1-5-2011 by plante1999]

[Edited on 1-5-2011 by plante1999]

ScienceSquirrel - 1-5-2011 at 16:49

Quote: Originally posted by plante1999

Here my review of the brauer NCl3 sol. synthesis with somme changes.

That is not a review of the reaction.
It is a video, lacking experimental detail, of the synthesis of a compound that can maim or kill the unwary.

plante1999 - 1-5-2011 at 16:56

Quote: Originally posted by ScienceSquirrel

Quote: Originally posted by plante1999

Here my review of the brauer NCl3 sol. synthesis with somme changes.

That is not a review of the reaction.
It is a video, lacking experimental detail, of the synthesis of a compound that can maim or kill the unwary.

It is why i said: ''this experiment should only be done by an experienced chemist''.

Also i should remade this video to insert more details , brauer synthesis is not very complete.

When the reaction was going i insert the chlorine with a plastic seringe to keep the pressure of chlorine safe , i also test the outlet gas for presence of chlorine , and the test show that tiny or no chlorine is present.

i will change my video , if you want to said
what detail is missing you thing. Im on science madness for learning wath is missing to my knowledge , and given my knowledge to those who need it.

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

ScienceSquirrel - 1-5-2011 at 17:48

Nitrogen trichloride is an explosive material that is arguably more dangerous than nitroglycerine.
You should have said: ''this experiment should only be done by a lucky chemist''.
Experience will minimise the risks but the material is unpredictably explosive so if enough people do it there will be inevitable accidents.
I would not encourage anyone to make this stuff and a video is just bonkers.

plante1999 - 1-5-2011 at 18:02

I will repeat but very deem reference tell that just to 18-20% it is safe solution (i made 12%). I know it is not safe as making copper carbonate but with safety messure it can be ok.

Somme people is very stupid and destroy the reputation of chemistry , take no safety messure and make 100% solution like this one , very stupid guy....

most stupid thing he do:

plastic tube
he dosn't wear gloves
very dirty worckspace , prone to said that chemistry is dirty
dirrect chlorine generator , no regulator
pur sol.

<iframe sandbox width="425" height="349" src="http://www.youtube.com/embed/YX5b_f0W3x0" frameborder="0" allowfullscreen></iframe>

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

Formatik - 1-5-2011 at 21:34

This is not the pure compound the guy wants to make. 12-15% solutions are harmless. But handeling them, I would use the same precautions like avoiding sunlight, cork, rubber, plastics (fluorine plastics are the exception maybe), fats, etc.

I've handled NCl3 itself several times and never had an accidental detonation. But I knew what precautions to take and the amounts weren't larger than dropper fulls (never absorbed the whole amount into the dropper).

Unless it were absolutely necessary for a chlorination, I would leave it alone also. Solution or not, NCl3 is an extremely nauseating compound. It has potential to contaminate large areas.

Sedit - 1-5-2011 at 21:50

LMAO I don't know how many times I have sounded exactly like that kid. ::stares at it for a second:: "What the Fuck!"... However I can assure you I would not be as excited as he was to spray toxic explosive shit all around my lab.

plante1999 - 2-5-2011 at 05:01

I just want to said that i prepare my synthesis 3 day in advence. and this guy make explosive on the fly .... I think the synthesis i made is prety safe (check 7 post up ther for the video )

also 2 thing:

After sommes test NCl3 chlorinate at RT titanium , very readily .

I remark that when i made chlorine in a seringe and i lubrify it with vegtable oil , i found that the oil is chlorinated to get a very stiky substance that become hard in 30minute.
for who want to know how i made the gas check this link:

http://mattson.creighton.edu/HowToPrepGases/Index.html

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

[Edited on 2-5-2011 by plante1999]

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[Edited on 3-5-2011 by plante1999]

plante1999 - 2-5-2011 at 16:14

Here a rewied tempory version of the synthesis i do , change because of the general opinion.

<iframe sandbox width="425" height="349" src="http://www.youtube.com/embed/3WFhJUt3GUw" frameborder="0" allowfullscreen></iframe>

Jor - 2-5-2011 at 16:47

I am considering on making a small amount of NCl3 solution and doing some experiments with it. However if I do this I will use even lower concentrations, I am thinking in the range of <10% and very small amounts <2-3mL solution). If I do this I will use CCl4 as it seems more stable and has a higher boiling point than NCl3, thus it is impossible it can somehow concentrate (wich could be possible with chloroform or DCM).
Can I also use cold acidified bleach (with HCl) to wich some conc. ammonia is added, followed by extraction with CCl4?
Is the NCl3 quantitively extracted in the organic layer? If so I would have to carefully calculate the amount of bleach I use to avoid too high concentrations.

Why does brauer use a 10-20% solution of CCl4 in CHCl3 as solvent?

You guys know some interesting reactions with the stuff?
Is it possible to swap the chlorine atoms in the NCl3 (in CCl4) with bromine atoms? NBr3 cant be made with ammonia as it will simply be oxidised to nitrogen.
How violently does it react with organics such as alkenes?
I wonder if it forms anhydrous metal chlorides from the oxides but I doubt it.

When watching the video with the accident it seems even if it explodes in solution it's not nearly as dangerous. A real high explosive would have shattered the glass in zillions of pieces and probably have killed or severely harmed the guy filming.
However if it was a solution in chloroform or CCl4 it would still have created huge concentrations of these solvents in the air.

[Edited on 3-5-2011 by Jor]

[Edited on 3-5-2011 by Jor]

plante1999 - 2-5-2011 at 17:08

From wath you said you should fallow my video , a the end i have 2.5ml of 12% sol. in CHCl3, i think you can replace the CHCl3 by CCl4. I do not think making chlorine dirrecly is safe....

In fact i made this chlorinating agent to make TiCl4 at RT, and it work.
I need to make more test to see if it make ligant with Transition metals.

I am searching other chlorinating agent, does anyone have idee of wath appen to vegtable oil with chlorine ( i know chlorination) because when i lubrify my seringe with it it become stiky and harden in 30minute.

From wath i see i do not think it is a solution he his making.

[Edited on 3-5-2011 by plante1999]

[Edited on 3-5-2011 by plante1999]

Jor - 2-5-2011 at 17:16

Plante I like your experiments but please do not scale this up and use NCl3 as a reagent to make chemicals. It can indeed be safe to experiment with the solutions but in to take no risk you really should not use any more than say 5mL (still contains more than 500mg of highly explosive substance) of this solution at once.

Can you hit a few drops of your solution with a hammer and see if it explodes? If even the bang of hammer doesnt do anything then I'm pretty sure it's quite safe.

plante1999 - 3-5-2011 at 07:58

Quote: Originally posted by Jor

Why does brauer use a 10-20% solution of CCl4 in CHCl3 as solvent?

You guys know some interesting reactions with the stuff?

Is it possible to swap the chlorine atoms in the NCl3 (in CCl4) with bromine atoms?

How violently does it react with organics such as alkenes?

I wonder if it forms anhydrous metal chlorides from the oxides but I doubt it.

[Edited on 3-5-2011 by Jor]

[Edited on 3-5-2011 by Jor]

Q:Why does brauer use a 10-20% solution of CCl4 in CHCl3 as solvent?
R: Probably brauer made this for geting higer boiling point of the solvent.

Q:You guys know some interesting reactions with the stuff?
R:I have teste the reaction with Ti and i am very happy because it work great , i will do a video in 1 week , Think youself , it is an chlorinating agent....

Q:Is it possible to swap the chlorine atoms in the NCl3 (in CCl4) with bromine atoms?
R:If you ad bromine , i think it work but i dont think it is a great idee.

Q:I wonder if it forms anhydrous metal chlorides from the oxides but I doubt it.
R:Tested with regent grade ZrO2 and it make small bubble , ive pass all my 2.5ml sol. , shit....

Q:How violently does it react with organics such as alkenes?
R:I dont want to try , with 5% sol ok but i dont want to kill myself.

Q:Can you hit a few drops of your solution with a hammer and see if it explodes? If even the bang of hammer doesnt do anything then I'm pretty sure it's quite safe.
R:Yes i will, when i will make an other 2.5ml.

affirmation: Plante I like your experiments but please do not scale this up and use NCl3 as a reagent to make chemicals.
R: I will never scale up this experiment and i only keep 2.5ml of this sol. , but if you already tried to make TiCl4 you probably know that it is more dangerous thant use 1ml of this sol to make it.

@Jor: Do you have tryed my synthesis of TiI4 if yes wath is the result?
I am working to make myself a data sheet , reaction , proprety and synthesis of 12% NCl3 sol..

[Edited on 3-5-2011 by plante1999]

[Edited on 3-5-2011 by plante1999]

[Edited on 3-5-2011 by plante1999]

Formatik - 3-5-2011 at 16:54

Quote: Originally posted by Jor

I am considering on making a small amount of NCl3 solution and doing some experiments with it. However if I do this I will use even lower concentrations, I am thinking in the range of <10% and very small amounts <2-3mL solution). If I do this I will use CCl4 as it seems more stable and has a higher boiling point than NCl3, thus it is impossible it can somehow concentrate (wich could be possible with chloroform or DCM).
Can I also use cold acidified bleach (with HCl) to wich some conc. ammonia is added, followed by extraction with CCl4?
Is the NCl3 quantitively extracted in the organic layer? If so I would have to carefully calculate the amount of bleach I use to avoid too high concentrations.

In my experience, an ammonium salt is likely to give better results than ammonia solution. Since, NCl3 is much denser than water and usually sinks in its preparation, it is likely that it falls into the organic layer.

Quote:

You guys know some interesting reactions with the stuff?
Is it possible to swap the chlorine atoms in the NCl3 (in CCl4) with bromine atoms? NBr3 cant be made with ammonia as it will simply be oxidised to nitrogen.

Yes, with aqueous bromide NCl3 is said to form NBr3, which is much more dangerous than NCl3. NBr3 can form from Br2/NH3 when the mole ratio is about 2:3, and the pH of solution less than 8. As noted in Gmelin, NBr3 is highly temperature sensitive and explodes at the slightest disturbance.

Quote:

How violently does it react with organics such as alkenes?

It depends on the organics. Many organics are chlorinated into detonation. There are certain organics it reacts (e.g. detonates) with, like simple fats (olive oil), or volatile substances like turpentine. Indirect contact with these, even underwater, causes violent detonation. Grease should also react. Materials like resins, lac, and rubber detonate it. Some soaps can also dangerously decompose it.

Gmelin points out that nitrogen trichloride doesn't react with alcohol, ether or benzene. Some references state benzene does react forming chloramine. Small amounts of chloramine (N-chloro-amines) have been noted to have formed when mixed with toluene or benzene.

I've made dilute solutions of NCl3 in methanolic dichloromethane, denatured alcohol (methanol containing), and toluene by dripping the NCl3 directly into those solvents. The hazard with more concentrated solutions could be due to too much nitrogen trichloride volatilizing out of solution undiluted. The dilute solutions generally react much less vigorously with compounds that make NCl3 detonate, e.g. you will see foaming, bubbles, and decolorization instead of detonation with something like olive oil.

I've studied a bit the reactions towards plastics in the small scale. NCl3 can be made in polypropylene beakers, but then part of the NCl3 penetrates deeply into the plastic and poisons the plastic. HDPE seemed equally as unreactive as polypropylene. Polystyrene clearly reacts, PETE also seemed to react but even more weakly than polystyrene.

I would expect a violent reaction with alkenes. In dilute solutions it can chloroaminate some. E.g., solutions have been used with 2-butene to give 2-chloro-3-dichloro-amino-butane. With trimethylethylene, amylene chlorides.

Quote:

I wonder if it forms anhydrous metal chlorides from the oxides but I doubt it.

This will usually convert it into nitrates and chloride under foaming. Aq. solutions of NaOH, KOH also decompose NCl3 forming nitrate, chloride and N2. I've dripped NCl3 into weak aq. NaOH, and seen the foaming reaction. Some metal oxides, e.g. PbO, CoO, CuO, Ag2O, Pb3O4 react similarly to weakly dilute alkali solution.

Quote:

When watching the video with the accident it seems even if it explodes in solution it's not nearly as dangerous. A real high explosive would have shattered the glass in zillions of pieces and probably have killed or severely harmed the guy filming.
However if it was a solution in chloroform or CCl4 it would still have created huge concentrations of these solvents in the air.

Nitrogen trichloride is a low order high explosive, I would not underestimate it.