Sciencemadness Discussion Board

I made solvated electrons without need of liquid ammonia

woelen - 13-8-2014 at 09:58

This is a very interestingt experiment which I want to share with you. Soon a web page will follow about this, but I now already want to let you know.

I purchased some lithium metal for a good price: http://www.ebay.nl/itm/281364082120?ssPageName=STRK:MEWNX:IT...

This lithium really is as clean and oxide-free as the picture shows. Fantastic stuff for a great price, I have given very positive feedback! I store it in an exceptionally well sealed bottle under pressurized butane gas. A few of these 'buttons' I keep in a smaller container, so that I do not always have to open the bigger container with the nice Li-sample.

I took appr. 2 ml of (nearly) anhydrous ethylene diamine in a test tube and added one piece of lithium (size appr. 8 mm length and 3 to 4 mm diameter). When this is done, then initially not much seems to happen. The piece of lithium becomes covered with a greyish layer, just as if it were kept in plain air for a few minutes.

After 5 minutes or so, however, small bubbles of gas are formed at the lithium, slowly. This gas must be hydrogen. The color of the lithium shifts to blue. When the test tube is swirled, then the blue color disappears but in a few seconds it becomes blue again. After another 5 minutes, there is much more blue material around the lithium and on shaking the blue color persists in the ethylene diamine, but it slowly disappears when the test tube is allowed to stand for a few tens of seconds. After a few minutes agian, a very dark blue solution is obtained and when the test tube is shaken, then a lot of the very dark blue liquid sticks to the glass. In a second or 3, the blue color simply disappears, while the liquid remains sticking to the glass. It is a very weird thing to see the liquid sticking to the glass losing its intense blue color in seconds and become colorless (somewhat opalescent white). This shaking can be repeated many times for many minutes. It is a very nice demonstration. I'll try to make a movie from this for my upcoming web page.

I also dropped a few drops of this intensely colored blue liquid in water. When this is done, then the drops at once lose their color when they touch the water, a soft hiss is produced (production of gas) and a clear soliution is obtained (ethylene diamine and LiOH in water).

The reaction must be as follows:

Li --> Li(+) + e

The Li(+) ions and the free electrons both are solvated by the ethylene diamine. The solvated Li(+) ion simply is colorless, the solvated electron is deep blue.

When the deep blue liquid is dropped in water, then the following happens:

2e + 2 H2O --> OH(-) + H2

Free solvated electrons cannot coexist with water.

The lithium ions do not react (except probably there will be ligand exchange from ethylene diamine to water).

The change of color from deep blue to colorless on the wall of the test tube is probably due to absorption of oxygen from the air:

4e + O2 --> 2 O(2-), which combines with the lithium and ethylene diamine to form a substituted amide and hydroxide:

O(2-) + NH2CH2CH2NH2 --> OH(-) + NH2CH2CH2NH(-)


Initially some gas is produced. This most likely is the reaction of lithium with a small amount of water in the ethylene diamine (it was sold to me as 99+ %, it most likely contains at least a few tenths of percents of water). Once the water is used up, then the solvation of free electrons occurs.

If you have pure ethylene diamine and a small piece of lithium (if it has an oxide layer, then just wait a little longer, but the experiment still works), then you really should try this experiment!

Loptr - 13-8-2014 at 11:19

I recall reading that amines are suitable solvents to solvate electrons. (I can't find the reference, but dug this up on wikipedia--I know).

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

Quote:

Focusing on ammonia solutions, all of the alkali metals, as well as Ca, Sr, Ba, Eu, and Yb, dissolve to give the characteristic blue solutions. Other amines, such as methylamine and ethylamine, are also suitable solvents.


Solvated electrons in solution are beautiful!

[Edited on 13-8-2014 by Loptr]

arkoma - 13-8-2014 at 12:10

Hmmm, I smell a Birch.........

Pretty nifty, Woelen. Shame the damned EU regs are gonna stifle your experiments soon. *sigh*

EDIT-it's come to my attention that my beginning statement might be misconstrued as thinking Woelen might be running a Birch Meth synth. NOT EVEN CLOSE to what I meant. Not to mention the fact that drug chemistry is not the "only" use of reductions. Woelen has mentioned the hazards of LiAlHydride--an empty baggie that had contained it caught on fire. Do I think he is making drugs? No. Get your minds out of the gutter peeps.

[Edited on 8-13-2014 by arkoma]

Edit--
Quote:
Modifications of the Birch reduction[edit]
Since liquid ammonia has to be condensed into the flask and has to evaporate overnight after the reaction is complete, the whole procedure can be quite troublesome and time-consuming. However, alternative solvents have been employed, such as THF[41][42] as well as a mixture of n-propylamine and ethylenediamine,[43] both with comparable results. The latter one actually is a modification of the Benkeser Reaction, which in its original forms tends to reduce naphthalene all the way to octahydro- and decahydronaphthalene.


from wikipedia

[Edited on 8-13-2014 by arkoma]

Brain&Force - 13-8-2014 at 12:38

I seriously hope we'll see a write-up on this soon! Solvated electrons with ethylenediamine is probably the only feasible method for me to do this.

There's a video of ytterbium dissolving in ammonia:

<iframe sandbox width="420" height="315" src="//www.youtube.com/embed/_-0BBk9CawU" frameborder="0" allowfullscreen></iframe>

[Edited on 13.8.2014 by Brain&Force]

Crowfjord - 13-8-2014 at 13:38

That's really neat, woelen! I've wanted to try this for a really long time, but have been quite wary of lithium and other alkali metals. I would love to try something like this for an actual Birch reduction (that's a synthesis of a 1,4-cyclohexadiene from a benzene, for those that do not know). Do you plan on trying something like that?

Here are a couple related threads:
http://www.sciencemadness.org/talk/viewthread.php?tid=10238
http://www.sciencemadness.org/talk/viewthread.php?tid=13161

[Edited on 14-8-2014 by Crowfjord]

sbreheny - 13-8-2014 at 20:56

Just curious - which EU regs are you referring to?
Quote: Originally posted by arkoma  


Pretty nifty, Woelen. Shame the damned EU regs are gonna stifle your experiments soon. *sigh*


arkoma - 13-8-2014 at 21:21

https://www.sciencemadness.org/whisper/viewthread.php?tid=23...

Burner - 14-8-2014 at 06:08

BTW, it appears that the eBay supplier that woelen used is selling Li through all the eBay boards. Here is the one for the US - http://www.ebay.com/itm/281364082120?_trksid=p2059210.m2749.... Based on woelen's positive experience I think that I will pick up some for my lab.

gdflp - 14-8-2014 at 06:14

Yeah, I've bought KI from that seller before. Shipping wasn't too bad considering it's coming from China and the price was excellent.

Loptr - 14-8-2014 at 06:26

Quote: Originally posted by gdflp  
Yeah, I've bought KI from that seller before. Shipping wasn't too bad considering it's coming from China and the price was excellent.


It's because of the ePacket. It's cheap, but can be slow. However, if that cuts the price significantly enough, then I am happy regardless.

MrHomeScientist - 14-8-2014 at 08:50

This is great work woelen, I'd love to see some photos of the process.

This lithium source looks amazing too. Normally I wouldn't buy from such a source (poorly described on eBay, comes from China, slow shipping) but if you've had a good experience I might give it a try. This is a very opportune time, because I'll be needing good lithium for my next set of experiments producing Nd metal!

gdflp - 14-8-2014 at 09:09

Quote: Originally posted by Loptr  


It's because of the ePacket. It's cheap, but can be slow. However, if that cuts the price significantly enough, then I am happy regardless.


Sorry, I wasn't very clear. All of their products have free shipping and the shipping time wasn't bad at 5-6 days. I've had ePackets take 4-5 weeks.

nezza - 16-8-2014 at 11:17

Does this experiment work with sodium ?.

Kiwichemicali - 16-8-2014 at 23:32

Quote: Originally posted by woelen  
http://www.ebay.nl/itm/281364082120?ssPageName=STRK:MEWNX:IT...

Interesting seller!

woelen - 17-8-2014 at 23:53

I have taken down my windows XP machine and switched to new hardware with Ubuntu 14.04. I moved my entire website source from the XP machine to the Ubuntu machine and now use Kompozer for editing web pages and Gimp for editing/scaling pictures. This works fine and I am quite happy with this. I, however, also made movies of the reaction with the free solvated electrons and I cannot find a good tool for editing videos (I used VirtualDub on my Windows XP machine). I installed Cinelerra, which is supposed to be a good video editing program, but I cannot make anything of this. Could someone please give suggestions to help me further with this issue. Right now I cannot edit videos and this is blocking further development of my website :(

Cinelerra is really overwhelming, I only need options for basic filtering (e.g. scaling down the resolution, rotating 90 degrees, 180 degrees or 270 degrees, taking certain intervals from the video, occasionally changing brightness and/or contrast, cropping, that kind of things). Cinelerra requires me to create a project for each video with a zillion options to be configured, but this sounds to me like a lot of complicated overhead. Do I really need to do that kind of complicated things for each simple video?

The system I am running is Kubuntu 14.04.1 LTS, which has a KDE desktop. The machine has an Intel Core i3, with HD4000 graphics, and 8 GByte RAM.

MrHomeScientist - 18-8-2014 at 05:42

Woelen, it sounds like you are looking for the same thing I wanted for my videos. I use AVS Video Editor: http://www.avs4you.com/AVS-Video-Editor.aspx

It's very basic and can be buggy sometimes (save often!), but it definitely does not have a lot of overhead at all. All I need is the ability to splice clips together, edit audio, display text, and make transitions, and this software works great for simple stuff like that. I have no idea what sort of system requirements it has, but you should definitely take a look. I'm pretty satisfied with it.

As an added bonus, with AVS you pay one time for a lifetime license and this gives you access to their whole suite of software, listed on the left of the page. Video, audio, and photo editing and even a DVD creator and some other goodies. All in all I think it's a very good deal.

woelen - 18-8-2014 at 10:07

Thanks for the suggestion, but this is not something I can use. There is no MAC/Linux support in this software. The software I use must run under Linux (Kubuntu). I found openshot. It is somewhat more intuitive than cinelerra, but it also has quite some limitations. E.g. cropping videos is a pain in the ass. On the other hand, editing in the time domain (e.g. splitting clips, creating cuts, keeping a single frame displayed for a somewhat longer time) is very easy. Rendering formats unfortunately are limited. I only can choose from some predefined resolutions (e.g. 720p, 1080p, DVD, VGA and some PAL compliant resolutions). With VirtualDub I could select any resolution, e.g. 720x1280 instead of 1280x720 for videos which are rotated 90 degrees. Still not really happy with this.

Brain&Force - 18-8-2014 at 10:34

Quote: Originally posted by nezza  
Does this experiment work with sodium?


I know sodium dissolved in ammonia will produce solvated electrons, but I don't know about ethylenediamine. Why not try it yourself?

I'm curious about how the lanthanides will react with ethylenediamine now, after seeing ytterbium dissolving in liquid ammonia.

[edit] woelen, do you have any images or videos I can add to the Sciencemadness Wiki's article on solvated electrons?

[Edited on 18.8.2014 by Brain&Force]

woelen - 18-8-2014 at 12:18

@Brain&Force: I will donate the pictures and videos of the solvated electrons, once I have resolved the software issues I have now with my website. I made a few nice videos of the solvated electrons and how they react with air and water, but at the moment they are not yet suitable for web publication (uncompressed 1080p videos, size well over half a GByte). I need to compress them, scale them down, do some cropping and do a little color correction (the videos are somewhat yellow, because I made them at artificial light with a color temperature of 5500 K).

@nezza: I can imagine that the experiment works with sodium as well. However, the reaction with sodium may be too exothermic, causing the solvent to boil away or causing the electrons to react with the NH2-group with formation of hydrogen and an -NH(-) ionic form (similar to amide, but with one hydrogen substituded).

Polverone - 18-8-2014 at 12:29

Quote: Originally posted by woelen  
Thanks for the suggestion, but this is not something I can use. There is no MAC/Linux support in this software. The software I use must run under Linux (Kubuntu). I found openshot. It is somewhat more intuitive than cinelerra, but it also has quite some limitations. E.g. cropping videos is a pain in the ass. On the other hand, editing in the time domain (e.g. splitting clips, creating cuts, keeping a single frame displayed for a somewhat longer time) is very easy. Rendering formats unfortunately are limited. I only can choose from some predefined resolutions (e.g. 720p, 1080p, DVD, VGA and some PAL compliant resolutions). With VirtualDub I could select any resolution, e.g. 720x1280 instead of 1280x720 for videos which are rotated 90 degrees. Still not really happy with this.


The easiest solution may be to install virtualized Windows XP under VirtualBox, since you already know a program that does what you need in XP.

unionised - 18-8-2014 at 13:21

"I made solvated electrons without need of liquid ammonia"
"The easiest solution may be to install virtualized Windows XP under VirtualBox"

Odd, I thought the easiest solution was to use ethylene diamine.

However I wondered if the isopropylamine from glyphosate based products might work too.




[Edited on 18-8-14 by unionised]

woelen - 19-8-2014 at 10:18

I tried the experiment with sodium. I cut a small piece of sodium from a larger lump, removed adhering oil with a tissue and dumped the piece of sodium in a test tube, containing 2 ml of ethylene diamine. Immediately, a very slow reaction starts, in which hydrogen is formed. The reaction is very very slow, giving tiny bubbles of hydrogen which make the ethylene diamine appear cloudy and only slowly move upwards.

I let this stand for 10 minutes or so. After 10 minutes nothing was changed. Still the very slow reaction at the surface of the piece of sodium in the ethylene diamine. The sodium sometimes goes to the bottom, sometimes it rises, due to adhering bubbles of hydrogen.

After another 10 minutes I added a tiny drop of water and swirled the test tube. When this is done, then the reaction becomes a little faster. Most remarkable is that the surface of the sodium turns blue, but the liquid remains colorless. Even after several minutes, the piece of sodium remains blue, but no color can be detected in the liquid. Slowly, when the water disappears, the reactions becomes slower and slower again, and the blue color becomes less intense.

I added another drop of water, this time a big drop from a faucet. Now, a much faster reaction occurs, the liquid turns warm (not hot) and the sodium becomes shiny/white, no blue color can be observed.

So, it appears that transiently, at the surface of the sodium, some solvated electrons are formed, but only when there is a very small amount of water present. In dry ethylene diamine, (hardly) no reaction occurs. The spectacular deep blue color, obtained with lithium, is not obtained with sodium.



[Edited on 19-8-14 by woelen]

Zyklon-A - 19-8-2014 at 10:32

Ah, that's a shame. I wanted to try that one. I guess I do have some lithium, so I could give it a shot.

nezza - 19-8-2014 at 10:44

The only liquid amine I have at the moment is aniline. I have tried adding a small amount of lithium to it and there appears to be no reaction. Next stop sodium.

woelen - 19-8-2014 at 11:12

Quote: Originally posted by Zyklon-A  
Ah, that's a shame. I wanted to try that one. I guess I do have some lithium, so I could give it a shot.
Even a small piece of lithium will do the job if your ethylene diamine is of good quality. If the ethylene diamine contains too much water, then you run the risk of having all lithium reacted with the water before any blue solvated electrons can appear.

Zyklon-A - 19-8-2014 at 11:16

But if it does contain some water (<2%) can I just use extra lithium? Or will the produced LiOH prevent the reaction somehow?

Brain&Force - 19-8-2014 at 11:22

2% shouldn't be enough to stop the reaction.

woelen - 19-8-2014 at 11:56

I think that using some extra lithium then will do the trick. First the lithium is used for removing the water and the resulting LiOH does not prevent further reaction. If you have 2% water in your ethylene diamine, then try with not more than 2 ml of liquid and a pea-sized piece of lithium.

Loptr - 21-8-2014 at 18:40


Lithium in Ethylenediamine: A New Reducing System for Organic Compounds
http://pubs.acs.org/doi/abs/10.1021/jo01359a009

Anyone have access?

Crowfjord - 21-8-2014 at 19:29

Bam

Attachment: jo01359a009.pdf (491kB)
This file has been downloaded 491 times

Also, here is one concerning Birch reduction with lithium and non-liquid ammonia. It is Turkish, though, so make of it what you will. Seems legitimate to me.

[Edited on 22-8-2014 by Crowfjord]

Loptr - 21-8-2014 at 19:47

Quote: Originally posted by Crowfjord  
Bam



Also, here is one concerning Birch reduction with lithium and non-liquid ammonia. It is Turkish, though, so make of it what you will. Seems legitimate to me.

[Edited on 22-8-2014 by Crowfjord]


Thank you! I thought this paper might be an interesting addition to what woelen had done already.

Loptr - 21-8-2014 at 19:54

According to the paper, sodium is used to purify (dry?) ethylenediamine, so it probably wouldn't substitute for lithium very effectively.

Quote:

Anhydrous ethylenediamine (Union Carbide Chemical Co. and Eastman) was purified by heating with sodium for a few days and then distilling; the reaction of sodium with t,he amine is slow.



woelen - 22-8-2014 at 14:37

Quote: Originally posted by Polverone  
The easiest solution may be to install virtualized Windows XP under VirtualBox, since you already know a program that does what you need in XP.

I wanted a solution in which I do not need Windows at all, but I gave up :(

I installed VirtualBox, installed Windows 8 in the virtual machine and installed virtualdub. This also was not an easy go. I needed to get suitable codecs. Now I have an aweful way of making videos for my website:
- First convert from MTS format to AVI format, using ffmpeg on my Ubuntu 14.04 box. In the same go, I convert audio from AAC 48 kHz to MP3 192 kb/s also at 48 kHz.
- I tranfer the files to my virtual machine and then I use virtualdub to scale the videos down, compress the videos to manageable size (from typically 100 MByte to appr. 5 MByte).
For Windows 8 there is no suitable MP3 encoding software, which integrates with virtualdub, hence the trick with ffmpeg under Linux, which uses Lame.

But I finally have a working solution. Now I can concentrate on the webpage itself and I hope to provide a webpage with pictures and videos very soon.

woelen - 23-8-2014 at 13:05

Finally, after a lot of struggles with new software for making videos and webpages, I have the webpage for the solvated electrons:

http://woelen.homescience.net/science/chem/exps/electride/in...

Now I have the software set up in such a way that in the future if I want to add other new pages, it should be a much easier process again.

papaya - 24-8-2014 at 02:41

wine+virtualdub?

bismuthate - 24-8-2014 at 04:58

do you think that aluminium (as an amalgam) could dissolve in liquid ammonia?
Also it would be very cool to try dissolving exotic metals like barium and europium in liquid NH3. I'll need to ask my mom for some dry ice.:)
EDIT: or get some ethylene diamine

[Edited on 24-8-2014 by bismuthate]

Brain&Force - 24-8-2014 at 19:02

I think you'll have success with lanthanides and liquid ammonia. Gadolinium and ytterbium are easy to come by (try Metallium), but I'm not sure they'll dissolve in ethylenediamine.

bismuthate - 28-8-2014 at 05:28

Do you think that europium would dissolve in ethylenediamine?

Brain&Force - 28-8-2014 at 10:29

I would think not, but it definitely will dissolve in liquid ammonia.

woelen - 28-8-2014 at 23:16

The smaller the solvent molecule, the easier the electride is formed and the more mobile the electrons are. Liquid ammonia is best, ethylene diamine works, but it works with less metals than ammonia. If you have access to anhydrous hydrazine, then it also is worth trying that (in small quantities!). Hydrazine is liquid at room temperature, so it is easier to handle. Hydrazine, however, is a nasty toxic compound, much more so than ethylene diamine.

A mix of ethylene diamine and n-propylamine seems to be one of the best things for electride formation at room temperature. Unfortunately, propylamine is not easy to obtain, it seems to be a precursor for some drug and I know of no supplier who sells that to non-registered individuals. Ethylene diamine, on the other hand, I can purchase without problems.

BromicAcid - 29-8-2014 at 03:29

If I recall correctly, hydrazine + alkali metals leads to explosion. Someone back me up on this please? Otherwise I will get a ref later.

smaerd - 25-6-2015 at 07:29

@woelen - Have you toyed with this experiment since then? Did you ever observe the bronze/reflective coloration with this solution?

woelen - 25-6-2015 at 11:05

I have tried other metals and I also tried lithium in ethylene diamine in a sealed test tube, so that oxygen is used up. In all these experiments I came no further than the dark blue species. The color becomes so intense that it almost is black, but I never saw the bronze-like appearance.

With other metals than lithium (K, Na, Ca) I had no success at all. The metals do not react. Apparently, the (en) only can dissolve the metal, if a sufficiently stable complex is formed and I think this only works for Li.

aga - 25-6-2015 at 13:39

Erm, solvated electrons ?

Blue in colour ?

Now i'm floundering like a beached whale.

j_sum1 - 25-6-2015 at 13:46

nice video on periodic table of videos. don't have time to look it up but it is worth it.


[Edit]
Here you go aga. http://www.periodicvideos.com/videos/liquid_electrons.htm
Knock yourself out!



[Edited on 25-6-2015 by j_sum1]

smaerd - 25-6-2015 at 15:19

@woelen - thanks for the reply and information. I'm really interested in this experiment. Your idea of using an n-propylamine ethylenediamine mixture for room temperature solvated electrons is a great one. I'd love to see that bronze color at room temperature. Maybe in the future I'll jump on board with tinkering here.

aga - 25-6-2015 at 22:01

Wow !

Thanks for the link j_sum.

Even a quick glimpse inside woelen's lab makes me feel like a baboon peeking into a starship.


[Edited on 26-6-2015 by aga]

j_sum1 - 25-6-2015 at 22:49

It doesn't matter how drunk you are, aga. You never lose the power of the simile.

gatosgr - 26-6-2015 at 02:02

What can you use this except reducing and what is the standard reduction potential for this reaction?