Sciencemadness Discussion Board

Making small amounts of liquid ammonia

mnick12 - 25-3-2010 at 19:02

So this is something I have been thinking about for a few days, and I am wondering what others think. As you all know Ammonia is a very useful compound, but working with it as a gas is very noxious and in certain cases undesireable. So I have been wanting to prepare a small amount of liquid ammona, and use it as soon as it is made. One might think why not just use ammonium hydroxide sol.?, but many reactions (like the one I plan on doing) are water sensitive. To be more specific I plan on reacting the ammonia with lithium to form lithium amide, and possibly sodium amide.

So my idea is this, and I may try this tomorrow or over the weekend. First generate ammonia gas in one vessel ( there are a number of ways to do this), then lead the gas into a dry ice acetone chilled graduated cylinder half full of toluene and hopefully the ammonia will condense in the toluene. Now I think this shold work, ammonia boils at -33 c. and dry ice is much colder than that, the only problem I see is that toluene freezes close to -91 so things may get tricky. So from there you could react with an alkaline metal of you choice.

Anyway I think this may work, and if I get my act together I will go ahead and try it out this weekend. If all goes well I will take pictures and post them.
here are some links I feel are relavent
http://en.wikipedia.org/wiki/Sodium_amide
and
http://www.sciencemadness.org/talk/viewthread.php?tid=13161

Mr. Wizard - 25-3-2010 at 19:39

Here are some links you may find useful.

http://en.wikipedia.org/wiki/Icy_Ball
http://crosleyautoclub.com/IcyBall/HomeBuilt/HallPlans/IB_Di...
http://free-energy-info.com/P13.pdf

pantone159 - 25-3-2010 at 19:45

These articles may be useful to you.

Attachment: solvated_electrons_ed800093n.pdf (676kB)
This file has been downloaded 1578 times

Attachment: solvated_electrons_ed800093n_si_001.pdf (493kB)
This file has been downloaded 1289 times

Sedit - 25-3-2010 at 19:59

Lithium in ammonia will not form Lithium amide which is a decomposition product of the Lithium complex formed in the solvated electron system. I posted the information there pictures and all. There is no need to form liquid NH3 since it forms a more concentrated product with less ammonia overall using a gas then when using a liquid and reacts in the same fashion.

If LiNH2 is your goal then you heat the Li complex or reduce styrene with it to yeild LiNH2.



Edit


Thank you for those papers.
This,
Quote:
The deep-purple solution at the onset of the noninhibited
reaction is replaced by a reddish-brown coloration incase of an
inhibited reaction


Might help explain the difference in coloration in successive attempts at forming the complex. The brown one is the result of using the new ADVANCED lithium batteries. Sounds like an inhibitor may be added to prevent cooks from using the new ones for birch reductions. This did not prevent formation of the complex but just added a strange coloration that was not there any of the other times i formed it.

[Edited on 26-3-2010 by Sedit]

Magpie - 26-3-2010 at 12:45

This may prove useful:

http://www.sciencemadness.org/talk/viewthread.php?tid=4566

mnick12 - 27-3-2010 at 10:59

Thanks for the papers and the threads, If I can get some dry ice today I will go ahead and try to liquefy some ammonia.
@Magpie- that is a very neet setup you have there, have you pursued it anymore? What I mean is have you made any more attempts at liquefying ammonia or pressurizing any other gasses?

Formatik - 27-3-2010 at 11:14

I've liquefied propane (Bp. -42 C) using dry ice, which I then used to form dry ice/liquid propane mixture in an attempt to freeze 91% isopropanol (it didn't freeze just became viscous and thick after several minutes). Even though it was liquefying well some of the stream invariably pushed vapors out of the partially covered container, the thiol smell was all over.

Be careful with dry ice and low freezing solvents. They can easily cause severe frostbite burns. Less than 2 drops of the chilled liquid propane dripped on my hand caused a severe burn that left a mark for several months.

[Edited on 27-3-2010 by Formatik]

Magpie - 27-3-2010 at 12:38

Quote: Originally posted by mnick12  


@Magpie- that is a very neet setup you have there, have you pursued it anymore? What I mean is have you made any more attempts at liquefying ammonia or pressurizing any other gasses?


No, as I really didn't have anything planned for the ammonia other than concentrating it. If I would have had some Na I would have dissolved it in the ammonia just to see the blue color. :)

woowhooo!

mnick12 - 27-3-2010 at 18:33

So I went and picked up some dry ice today and attempted the lithium ammonia complex. Without to much effort I was able to do it. I started out by measuring 20ml of hexane and placing it in a 100ml graduated cylinder next I measured 100ml of 99% isoproply alcohol and poured it into 250ml beaker. I placed the cylinder into the beaker and added dry ice chunks to the alcohol. Next I setup my ammonia generator by decomposing urea into ammonia and biuret. For the lithium I used the metal from one energizer battery which I think is around .91g I dont remember, and placed this in the hexane. The volume now was close to 22ml, and I then started bubbling ammonia into the hexane. At first nothing happened and a lot of gas was escaping so I added more ice to the alcohol. Bubbling ceased and the lithium turned a greyish-blue, then the volume began increasing and the whole thing turned a dark color with little copper colored specs floating in it. I figured it was done so I took out the gas source and aloud the lithium mix to warm up to room temperature, and while it was warming it evolved a large amount of ammonia gas. I ended up with a solution that was now 30ml in volume (opposed to 21ml original), and it separated into two layers coppery lithium bronze on top and a greyish substance on the bottom. So it worked well but I am a little confused as to what the greyish stuff at the bottom is, could it be lithium amide?

Anyway here is a pic of the final product


lithium bronze.jpg - 43kB
enjoy! and comments are appreciated

Magpie - 27-3-2010 at 19:35

Well done. From my reading of Wiki it seems you have succeeded in solvating some electrons!

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

BTW, what is the purpose of the hexane?

[Edited on 28-3-2010 by Magpie]

Sedit - 27-3-2010 at 20:56

Nice its pretty isn't it:D. Get some in an eye dropper and watch it turn from Gold to redish gold to deep blue in front of your eyes its a sight to behold. Iv always assumed that the white is LiOH from damp NH3 but I could very well be wrong.

This is very stable if capped and stored in the cold. Alot more stable then I thought it would be. Alcohol rapidly decomposes it with a violent hiss and a rapid release of NH3.

Also im sure its more efficient to use the cold dryice slurry but it is in no way needed and an Ice/salt water bath works just fine.

Congrates once again its cool to see someone else reproducing this as well. Last time I went to make it I found dry NH4NO3 is shitty for NH3 generation and just forms a clump that sits there doing nothing.

mnick12 - 27-3-2010 at 23:09

Thank you Magpie and Sedit,
For a while I thought about reducing something like styrene to produce lithium amide and ethylbenzene, but the stuff is so darn neet looking!It looks like liquid copper that is not red hot. But I may have to do something with it before it starts decomposing, does ethylbenzene have any interesting chemistry? Or is it kinda useless? Another thing that suprised me was how easy this synth was, I mean I usually have to try something like 4 times before it actually works. I think tomorrow I may get some more ice and more lithium and scale it up.

Magpie- The reason why I used hexane was to allow the ammonia to contacts something cold for the longest ammount of time possible. I guess it is not necessary I just thought it would help the yield. And all the articles I read mentioned storing it in a hydrocarbon, and I did not have any toluene.

unionised - 28-3-2010 at 04:37

Re Formatik's post
"Be careful with dry ice and low freezing solvents. They can easily cause severe frostbite burns. Less than 2 drops of the chilled liquid propane dripped on my hand caused a severe burn that left a mark for several months."

How much less than 2 drops was it?

watson.fawkes - 28-3-2010 at 07:20

I interject to recommend again the article I posted here for more information on lithium-ammonia solution. For fans of physical chemistry, it's a gold mine, particularly the sidebar that begin on p. 8218. That bronze-colored solution is a proper metallic state. As the authors say: "At saturation σ~1.5 x 10^4 Ω^-1 cm^-1. In terms of atomic conductance, this is higher than mercury at room temperature."

Sedit - 28-3-2010 at 07:50

I highly recommend that artical that watson posted. I go over that paper atlest a couple times a week and still have yet to take in all the data the so nicely present.

I know its a side note but given its conductance compaired to Hg has anyone ever tested this substance for super conducting abilitys. Hg was one of the first substances to display this property after being chilled with liquid helium so I wounder at what temperatures this substance would display that ability. Can this substance be frozen?

Perhaps we could merge this with the other thread since it is the same topic and experiment.
Quote:
For a while I thought about reducing something like styrene to produce lithium amide and ethylbenzene, but the stuff is so darn neet looking!


You read my mind:D . Your in a hurry to use it but trust me it stores for weeks on end.

UnintentionalChaos - 28-3-2010 at 09:11

From here: http://www.freepatentsonline.com/5486343.html

"After at least one equivalent of ammonia was added to the reaction mixture, it was heated to a temperature between 50° and 80° C. to decompose the lithium bronze to form a gray suspension of the product lithium amide in the solvent. The product was recovered from the reaction solvent, washed several times with a hydrocarbon solvent and dried in a stream of argon gas to afford a free flowing white powder."

Sedit - 28-3-2010 at 13:01

Quote:
But I may have to do something with it before it starts decomposing


I just got an idea and its something I wanted to try but never got around to doing it. The bronze complex is known to reduce many metal oxides to there base metals so I was thinking how about chlorides. Why not attempt to use a small amount of the complex on NaCl since it may very well produce Sodium metal. I would think at the very least you should be able to produce the Sodium variation of this substance.

Disaster! (sorta)

mnick12 - 28-3-2010 at 14:02

Sedit, that sounds like a good idea I am currently making one more battery's worth of lithium bronze. If I can isolate some of the bronze I will react with some NaCl, and I will video tape it and post on youtube then link it in my next post. And if I have enough money I will order some sodium and maybe sometime in the next few weeks I will make some sodium bronze. Thanks for the paper Chaos and watson.
Oh does anyone know what the reaction with alcohols is? I know it reacts with alkyl halides to make amines, but how about plane alcohols?


So I do not think this deserves a whole new post so I am just gunna edit it in.
Ahhh with so much going well yesterday I guess it is only fair something went wrong today. So I added another sheet of lithium to the bronze hexane mix from yesterday and began adding ammonia. Everything was going well so I went to go clean out an old flask. Then I heard a small plump noise so I ran out and to my shock and horror the beaker holding the flask fell over!I am not sure how much of the actual bronze was lost but looking on the table I would say at least 3ml:mad:. I then refilled the flask with hexane and added more urea to the ammonia generator. I hope that was not all of it I will be able to tell later.

[Edited on 28-3-2010 by mnick12]

UnintentionalChaos - 28-3-2010 at 14:08

Quote: Originally posted by mnick12  
Sedit, that sounds like a good idea I am currently making one more battery's worth of lithium bronze. If I can isolate some of the bronze I will react with some NaCl, and I will video tape it and post on youtube then link it in my next post. And if I have enough money I will order some sodium and maybe sometime in the next few weeks I will make some sodium bronze. Thanks for the paper Chaos and watson.
Oh does anyone know what the reaction with alcohols is? I know it reacts with alkyl halides to make amines, but how about plane alcohols?


As the bronze behaves like metal for the most part, I suspect it's merely a deprotonation forming the alkoxide and releasing NH3.

Formatik - 28-3-2010 at 14:18

Quote: Originally posted by unionised  
Re Formatik's post
"Be careful with dry ice and low freezing solvents. They can easily cause severe frostbite burns. Less than 2 drops of the chilled liquid propane dripped on my hand caused a severe burn that left a mark for several months."

How much less than 2 drops was it?


It might have even been about one drop. It wasn't much at all.

Garrrrrr!

mnick12 - 28-3-2010 at 15:39

Since the accident I only have a few small beads of lithium bronze so it looks like I wont have enough to do the sodium test. But on the bright side it looks like I have maybe 1-2 grams of lithium amide. I may revisit this later, I encourage people to try this reaction it is fairly simple and gives a very neet product, something that looks like copper red mercury!