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froot
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Nitrogen trichloride NCl3 production
I've seen discussions here involving this nasty stuff but a possibly stupid/interesting question still prods my curiosity.
I'm lead to believe that NCl3 can be made by bubbling Cl gas through NH4NO3 solution.
If one product is NCl3, could the other possibly be HNO3 under the correct conditions?
I'm wondering if there's a route using heat, a catalyst and a different solvent?
EbC: Edited title.
[Edited on 9-9-2006 by chemoleo]
We salute the improvement of the human genome by honoring those who remove themselves from it.
Of necessity, this honor is generally bestowed posthumously. - www.darwinawards.com |
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Theoretic
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Nooo... no heat, no catalyst, you're dealing with NCl3! I take to it you don't fully know the stuff... it's extremely heat/catalyst
sensitive. The reaction you're proposing will run easily, in aqueous solution, and produce not simply HNO3, but a 3:1 (in moles) mixture of HCl +
HNO3 - i.e., aqua regia...
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S.C. Wack
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Keep in mind that its discoverer, Dulong, lost three fingers and an eye from this. Davy, very aware of this, was knocked senseless by a small amount
on his first cautious try, and was surprised by the damage done.
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The_Davster
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I have aparently once made some NCl3 acidently. After only being around it once for a very short period of time, I must say the sensitivity(even in
solution) and how powerfull it is really surprises me.
Here is what happened http://www.sciencemadness.org/talk/viewthread.php?tid=2044
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Proteios
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| Quote: | Originally posted by S.C. Wack
Keep in mind that its discoverer, Dulong, lost three fingers and an eye from this. Davy, very aware of this, was knocked senseless by a small amount
on his first cautious try, and was surprised by the damage done. |
The moral is..... think long and hard before doing anything that may be....irreversible.
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mbrown3391
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Nitrogen Trichloride from Urea
Could anyone tell me the chemical reaction that occurs when urea is mixed with sodium hypchlorite (NOT in the presence of sodium hydroxide) that would
yeild Nitrogen Trichloride? Also would this reaction have to be cooled, heated, or left at room temperture in order to yeild NCl3?
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12AX7
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H2N-CO-NH2 + 7OCl- + H2O = CO2 + Cl- + 2NCl3 + 6OH- (I think that balances)
Since chlorine is removed by chlorination, charge is conserved by forming hydroxyls, so this will be driven by reducing pH, and should be stable at
that (assuming it doesn't overreact and go high in pH, unchlorinating the product, but that doesn't really make sense). I mean, stable such as NCl3
is...
Don't know about thermodynamics.
Tim
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mbrown3391
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If the reaction yeilds sodium hydroxide, what stops hydrazone from being formed instead of NCl3?
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12AX7
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Hydrazone?? Would that be, erm, H2N-(N(+)=O)-NH2, i.e. the nitrogen analogue of acetone? But I've never heard of that so I assume you typoed
hydrazine.
Should be that NH2- radicals form when the carbonyl is attacked (forming CO2), and they bond together to form hydrazine, which is further oxidized to
N bits which chlorinate. Just a matter of carrying it farther.
Tim
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mbrown3391
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Yes i did mean hydrazine. Would a large amount of household bleach be sufficient for this reaction, or would i have to chlorinate some sodium
hydroxide? Also, i think household bleach contains traces of sodium hydroxide left over from production. Would this effect the reaction? Finally, at
what tempurture should the reaction be kept?
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mbrown3391
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| Quote: | Originally posted by 12AX7
H2N-CO-NH2 + 7OCl- + H2O = CO2 + Cl- + 2NCl3 + 6OH- (I think that balances)
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The oxygen doesn't balance actually. There are 9 oxygen atoms on the left and 8 on the right. Maybe it's this?:
H2N-CO-NH2 + 6OCl- + H2O = CO2 + 2NCl3 + 6OH-
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12AX7
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Thanks, that hanging Cl didn't quite make sense. 
Of course you can also add another H2O and form CO3(2-) + 2H+, killing two OH-, but it's still a pretty basic result (4 mol OH-, plus an ionized
carbonate).
Tim
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Marvin
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Not that this isn't a wonderful game of scrabble you are having here....
mbrown,
Why do you think mixing sodium hypochlorite with urea will produce nitrogen trichloride?
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mbrown3391
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Searching "urea" +"nitrogen trichloride" on google brings up countless pages that say mixing urea with sodium or calcium hypochlorite will form
nitrogen trichloride. Heres one example:
http://www.jtbaker.com/msds/englishhtml/U4725.htm
| Quote: |
Incompatibilities:
Urea reacts with calcium hypochlorite or sodium hypochlorite to form the explosive nitrogen trichloride. It is incompatible with sodium nitrite,
gallium perchlorate, strong oxidizing agents (permanganate, dichromate, nitrate, chlorine), phosphorus pentachloride, nitrosyl perchlorate, titanium
tetrachloride and chromyl chloride. |
Upon mixing small amounts of Clorox bleach and urea, i did observe the evolution of a gas. As 12AX7's chemical equation shows, CO2 gas would be
evolved when urea and sodium hypochlorite are mixed. At the very least, a chemical reaction did occur. So, if it does not produce nitrogen
trichloride, what does it produce?
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Marvin
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No, when you arrange the symbols to match the chemistry, that is a chemical equation. When you arrange letters for the purposes of getting things you
recognise, that is scrabble.
An MSDS will list a lot more than quantitive reactions, it will list side products and rare events.
The actual products will depend a lot on circumstances, concentration, ratio of reactants. Simply thrown together in the 'expected' ratios for
nitrogen trichloride, I would expect large amounts of carbon dioxide and nitrogen gas, some liberated chlorine with a possiblity of a non zero amount
of NCl3. Assuming the mixture can get acidic enough. NCl3 forms only in slightly acid mediums and is removed by OH- or by reaction with ammonia, or
urea.... Reliable means for making NCl3 are in another thread.
Classically the Urea and Hypochlorite reaction is the industrial synthesis of Hydrazine, a modification of the Rashig process.
[Edited on 3-9-2006 by Marvin]
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JohnWW
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Does anyone in New Zealand want some urea? I recently bought a box of it in an auction in small plastic bags, intending to use it as a fertilizer. and
I have some surplus.
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mbrown3391
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Nitrogen Trichloride through Electrolysis
I have read that it is possible to produce nitrogen trichloride through the electrolysis of an aqueous solution of NH4Cl. Can anybody explain the
reaction which would occur during this process, if it is even possible?
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hodges
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See
http://www.sciencemadness.org/talk/viewthread.php?tid=2397
Hodges
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hodges
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Doesn't hurt to post this link as to what can happen when you accidentally form nitrogen trichloride (from hypochlorite and urea, no less):
http://www.chemaxx.com/explosion16b.htm
Hodges
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mbrown3391
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I used followed your link, hodges, and i found this:
| Quote: |
"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" |
I tried mixing small ammounts of the above chemicals and i did see a yellow precipitate. I then dripped a single drop of the supposed NCl3 onto a
peice of paper and put a drop of turpentine on top of that. Nothing happened. I tried adding terpentine directly to the test tube. Still nothing
happened.
Can anyone verify that the above chemical equation is accurate? If so, why can't I get the extremely senative NCl3 to detonate?
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hodges
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Mbrown, what did you use for your 70% CH3COOH?
You may be lucky it didn't detonate - I've heard stories of a tiny drop shattering containers and removing fingers when it detonates. I certainly
wouldn't want my body anywhere near it when it detonates - which is why I placed oil on a long stick for my experiment, and even that a very small
calculated amount based on the amount of current passed through during electrolysis. With larger quantities like it sounds like you were making I
would not even want to be that close.
You may want to try making nitrogen tri-iodide instead. This is (relatively) much safer. There is plenty of information on nitrogen triiodide here
and on the internet in general.
Hodges
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mbrown3391
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I substituted the correct amount of 5% white vinegar for the 70% acetic acid. I thought it might not work, but since i did see a yellow precipitate i
assumed that it.
Don't worry, i wasn't following those instructions exactly i used about 1 ml of bleach, 2 ml of vinegar and 1 ml of ammonium chloride.
And i have already made Nitrogen tri-iodide multiple times. It is just as interesting, but much more expensive as it requires iodine crystals.
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hodges
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I think the viengar is your problem - not nearly strong enough. You might want to try muriatic acid instead. There is nothing special about viengar
in the reaction - I'm sure it was just chosen for expediency. You could use sulfuric acid as well but that would be even more dangerous because of
all the heat it gives off when diluting.
Hodges
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mbrown3391
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What would the chemical equation be, and is the HCl just a catylist or part of the reaction?
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mbrown3391
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The case is closed on Nitrogen Trichloride production. There are many methods for creating it, most of which have been outlined in this topic, and for
me all failed except for this one:
HCl is reacted with ammonia to produce NH4Cl. Additional HCl is added which (I assume) will later act as a catylist. A small amount of NaHCO3 is added
to be sure the liqud contains excess HCl. The liquid is then placed in a plastic testube or beaker (NO GLASS!) and placed in an icebath. When the
liquid is cooled well below room tempurature, 6% NaOCl is slowly dripped in. Immediately the liquid should become yellow and cloudy. Continue to add
bleach until the liquid is completely opaque. Allow it to settle in the icebath. Within 5 minutes you will begin to see a distinct seperation between
a cloudy layer and a transparent layer. The cloudy layer is NOT the finnished product! Within fifteen minutes you should begin to see tiny distinct
droplets of a yellow oil on the bottom of the container. When the reaction is complete the solution will be completely clear with droplets of oil on
the bottom.
I beleive the equation would be
-----------------------HCl
3NaOCl + NH4Cl = NCl3 + NaOH + HCl
NCl3 + NaOH + HCl = NCl3 + NaCl + H2O
If the reaction gets out of hand dump it into a cup of ammonium hydroxide, which destroys the NCl3
I beleive one could make NI3 by mixing NCl3 with KI, but i may be wrong.
NCl3 + 3KI = NI3 + 3 KCl
The advantage of this is that Potassium Iodide is much more readily available than Iodine crystals.
[Edited on 10-9-2006 by mbrown3391]
[Edited on 10-9-2006 by mbrown3391]
[Edited on 10-9-2006 by mbrown3391]
[Edited on 10-9-2006 by mbrown3391]
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