Sciencemadness Discussion Board

Explosive reaction, discovered by 'luck'

woelen - 16-4-2010 at 12:03

When I experiment with bromine vapor or chlorine gas then I use dilute ammonia for cleanup purposes. This is a perfect way to cleanly get rid of bromine vapor (making N2 and NH4Br) and an almost perfect way to cleanly get rid of chlorine (making N2 and NH4Cl and a tiny amount of NH2Cl as a side reaction).

Yesterday I had a test tube full of ClO2 gas and I thought that this also simply could be destroyed by adding some ammonia. Indeed it can be destroyed by adding some ammonia but this goes in a somewhat more spectacular way than the destruction of Br2 and Cl2 :D.

Have a look at this webpage: http://woelen.homescience.net/science/chem/exps/NH3_ClO2/ind...

If you have some chlorate and conc. hydrochloric acid you can do this experiment yourself. If you have chlorite (less common than chlorate) then you can do really spectacular things.

franklyn - 17-4-2010 at 16:50

Never know what you may find
http://www.crscientific.com/article-redox3.html

.

bquirky - 18-4-2010 at 03:30

I had a small explosion the other day i wasn't expecting.

I was trying to reduce copper oxide using glycerol on mild heat in a small (50ml) beaker. nothing at all for about 10 minutes and then *BANG* glycerol coated copper oxide and copper powder EVERYWHERE! what a mess !

i haven't been able to work out what happened if it was a superheated pocket at the bottom of the beaker that expanded or if it was actuly the reduction reaction itself that runaway.

took long enough to cleanup though :)

woelen - 18-4-2010 at 03:48

@bquirky: I think that it is the superheating. I also have done numerous reductions of copper(II) to copper(I) with glycerol (CuCO3, Cu(OH)2 and CuO) and always this reaction seems to be very slow and additional alkali needs to be added to have an acceptable reaction rate.

@franklyn: I know that reaction, I discovered it myself quite some time ago and together with a Belgian apothecary I partially resolved the problem: http://woelen.homescience.net/science/chem/riddles/copper+th...

Link to site really helpful for this newbie

SWilkin676 - 19-4-2010 at 07:39

Thanks for posting the link to that site it's really helpful to me - would recommend it to all newbie chemists!

I've been watching all the videos of things that go boom - aside from the desire to try this at home, I'm getting a healthy respect for all those little vials of metal powder in home lab.

MSDS's tend to have a negative effect on safety for me because when I first started working with chemicals they made everything sound so lethal that I was handling things with a full moonsuit that didn't need it. My partner has been playing with this stuff all his life and therefore he makes things look less dangerous than they are.

It's hard for me to really believe in things like reactivity of metals and chemicals because I have never seen what happens when certain things get mixed. At first I was afraid of everything and now I've gone too far the other direction. For example, I was studying some of our chemicals, noting the color, texture, etc and shook one of the jars slightly to get a better look at the crystals - then noticed the label said don't shake! So I need a better respect for this stuff.

Great link. And very educational post.

[Edited on 19-4-2010 by SWilkin676]

Melgar - 20-4-2010 at 17:25

Actually, it seems a certain Pierre Louis Dulong beat you to it.

http://en.wikipedia.org/wiki/Nitrogen_trichloride

"Nitrogen trichloride is a dangerous explosive, being sensitive to light, heat, and organic compounds. Pierre Louis Dulong first prepared it in 1812, and lost two fingers and an eye in two separate explosions. An explosion from NCl3 blinded Sir Humphry Davy temporarily, inducing him to hire Michael Faraday as a co-worker."

You may want to try other ways of getting rid of the halogen vapors. I admit this may not have been the product of your reaction, in which case, let's hope it stays that way. ;)

chemrox - 20-4-2010 at 18:17

what's a good avi player that isn't a MS product?

not_important - 20-4-2010 at 19:23

Try VLC http://www.videolan.org/vlc/

woelen - 17-5-2010 at 13:24

I stumbled upon this seller for sodium chlorite, who ships the material worldwide (except some USA-locations) and this might be interesting for many of us. People in the USA might want to look at their own eBay, which has many sellers of sodium chlorite, who only ship to USA-locations.

http://shop.ebay.nl/naclo2009/m.html?_nkw=&_armrs=1&...

This is a really interesting chemical and with this post I hope I can help some others as well. I also ordered from this guy (look at his feedback list, then you'll see me) and I am very happy with his product.

The WiZard is In - 17-5-2010 at 13:39

Quote: Originally posted by Melgar  
Actually, it seems a certain Pierre Louis Dulong beat you to it.

http://en.wikipedia.org/wiki/Nitrogen_trichloride


---------
The Iranians pests are working on astatine chloride
because it is both explosive and radioactive.

chief - 18-5-2010 at 01:54

Nitrogen Trichloride can be made by electrolyzing NH4Cl ; but it's far too dangereous ...
==> Just one of the reasons _not_ to electrolyze NH4-compounds ...

Interesting method

a_bab - 18-5-2010 at 04:34

This is a "russian" method (I can't credit the original author who wrote this but I do know he is russian and he posted it on the now defunct EWF)

It allows scaling up and give more chances to get rid of "useless" limbs. Just imagine what some organic traces would do... In the original thread there was a mention of an "accidental" explosion that hapenned during the night to someone who attempted to do it, and it was pretty much the equivalent of NG drop for drop. Gotta find it in the E&W archive. If I can get an archive, that is.

Attachment: NCl3.txt (1kB)
This file has been downloaded 745 times

Formatik - 18-5-2010 at 17:39

Those vague methods are very dangerous, I wouldn't follow them. There is enough information in the nitrogen trichloride thread to allow safer microscale preparation in much smaller amounts. Though even that thread doesn't have enough saftey information on NCl3. Then again, neither does a lot of literature on its preparation and experimentation. There is a lot that can make it detonate. Doing something as mundane as attempting to pick it up with a glass dropper with a rubber bulb can cause detonation, since rubber detonates it. The formation conditions are also sensitive and similar reactions are seen with bromine and NH4+ in formation of bromamines. Brauer shows preparation in larger scale with safer dilute NCl3 solutions.

Concerning ClO2 and NH3, Gmelin doesn't mention the energetic reaction, just products of interaction: Stadion (Gilb. Ann. 52 [1816] 210): mixing ClO2 with gaseous NH3 forms NH4Cl, NH4ClO3, H2O.

Cl2 and NH3 can form various toxic chloramines, maybe some N2H4, also harmless NH4Cl. Anhydrous reactants can form NCl3 also, or if lightly acid. The NH3 should always far outnumber the Cl2. NH3 destroys NCl3 and all the other chloramines as it reacts with them. If it weren't for this, the reaction to prepare hydrazine which use large excess of ammonia, from ClO- and NH3 would be much more dangerous. NH3 can explode NCl3, but this shouldn't be a problem especially in the gaseous phase, with unaccumulated, unformed NCl3. So Cl2 is made "less persistent" with ammonia by converting it to these compounds.

Globey - 4-6-2010 at 16:13

look at all those hydroxyls which want to be pulled off glycerol simultaneously. I imagine that could be quite a pop going offl just guessing. you sure you didn't make something like NCL3?

[Edited on 5-6-2010 by Globey]

Anders Hoveland - 7-7-2010 at 10:50

I wonder how ClO2 would react with Cyanuric acid ? Unlike chloramine, trichloroisocyanuric acid is resistant to further oxidation by Cl2.
a OClO--N(COR2) might form or even O2Cl--N(COR)2.

current industrial route to Cyanuric acid (CNOH)3 entails the thermal decomposition of urea, with release of ammonia. The conversion commences at approximately 175 °C (wikipedia)

chlorination gives Sodium dichloroisocyanurate, then trichloroisocyanuric acid, [C(O)NCl]3

stygian - 7-7-2010 at 17:26

Quote: Originally posted by bquirky  
I had a small explosion the other day i wasn't expecting.

I was trying to reduce copper oxide using glycerol on mild heat in a small (50ml) beaker. nothing at all for about 10 minutes and then *BANG* glycerol coated copper oxide and copper powder EVERYWHERE! what a mess !

i haven't been able to work out what happened if it was a superheated pocket at the bottom of the beaker that expanded or if it was actuly the reduction reaction itself that runaway.

took long enough to cleanup though :)



From roguesci, by PH Z iirc, quoted elsewhere here. May be relevant.

"Lead glycerolate can be done by boiling excess glycerol with lead hydroxyde (1/2hour)
CH2OH-CHOH-CH2OH + Pb(OH)2 --> CH2OH-CH(O-)-CHO-Pb + 2 H2O
Filtrate the white precipitate (Pb(OH)2 is also white so it appaers nothing has happened but stil) wash with water several times and allow to dry at 40-60C.
The dry compound deflagrates when heated confined."