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Sedit
International Hazard
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Preparation of Lithium Ammonia complexes in EtO2.(Lithium Bronze)
I think my memory may have failed me after a year and may have provided slightly inaccurate data to Len1 and UC. After the discussion VIA PM with
UnintentionalChaos I think -38 degrees F was the temperature reaches almost everytime in my snow+HCl experimentation however with the addition of more
snow and stirring the temperature could be push as low as -42 with ease. Sorry for the confusion but these experiments where quick and dirty and
performed almost a year ago.
With that being said I decided to run the reaction again since I got about 16 inches of material to work with now but to my disappointment I found the
battery of the thermometer is now so dead that you can not even get it to stay on let alone read the faint numbers present on the screen.
This was a blessing in disguise as it turns out. What I decided to do was setup a three test tube system in an attempt to liquefy Ammonia using this
super cold mixture. Prior attempts last year provided a frost which sublimed on heating to "room temperature"(26 degrees outside at the time). This
made me think that my thermometer was tweeking out since it was past its lower end of -32 and that quite possibly it was freezing the Ammonia.
Feeling that this was unlikely(although Nitric acid reportedly reaches like -97 IIRc) and more then likely due to trace H2O Binding the NH3
into the frost I seen So I decided to add a drying tube in between the flask this time which consisted of EtO2 and much Excess of Lithium
in the Ether to ensure the exiting gas was sufficiently dry. This was more exciting and successful then I could have ever hoped for.
Setup:
Test Tube A: NH3 generator by adding powder NaOH to NH4NO3 Mixing completely and stoppering with a tube coming from the top of A
leading into the bottom of B. When in operation a few drops of over the counter dilute aq Ammonia was added to initiate the reaction and this was
placed in a warm water bath placed on a warming plate.
Test Tube B: Ether straight from the can, enough to cover Lithium from one half of a AA Lithium Advance battery. Lithium was dipped in other starter
fluid to remove mineral oil it was stored in then patted dry before quickly chopping it up to the side of small BB's[note1]. A tube ran out of the top
of B and down to the bottom of C
Test Tube C:
Lithium prepaired as stated above was placed in the bottom of the test tube with only a ml or so of EtO2 to aid in thermal transfer.
Test Tube C and Test Tube B Where both placed in the super chilled HCl/Snow mixture.
Procedure
Test tube C was placed in an HCl/Snow slurry and the whole setup was sealed and initiated with a few drops of aq ammonia to start the NH3
production. Ammonia gas bubbling into Vessel B commenced rapidly as the Lithium beads begun to quickly take on a noticeable copper color which
proceded to bright gold as the reaction progressed.
Results:
Test tube A obviously produced Sodium Nitrate + H2O + NH3 this was not quantified. Test tube B Is where the unexpected happened.
As the reaction progressed I expected that the ammonia would form a while powder due to its reaction with H2O making LiOH and H+. This did
indeed happen and you can see some Of the white powder on the bottom of the test tube. What is interesting though is the fact that the Ether itself
begun to take on a slight blue color which quickly darken to an almost royal blue color similar to that of the toolbar at the bottom of a Windows OS
system. Ill try to think of a better way to describe it since many may not understand what I'm talking about due to variances in computer systems and
settings but as of now that's the best I can do. I have seen references to Crown ether's being used at low temperatures for solving electrons but that
is normally well below -38f or -42 and somewhere in the range of -78degrees C If I recall correctly. I believe chilled EtO2 with a little
bit of solvat ed ammonia can accomplish this at a much higher temperature then previously reported. Further test will be performed tonight conditions
pending
Test tube C Showed signs of condensate on the sides of the test tube eventually coalescing into a clear fluid liquid at the bottom of the test tube
which in short time took on a dark blackish blue color due to the Lithium present "solvating" the electrons. In with this was the same Gold liquid
noted in flask B Proving the excess Li that was added to the liquid Ammonia which condensed was also forming the Li[NH4]x complex also noted in
literature as Lithium bronze.
Pictures..... Because everyone loves picture I was only about to get the middle vessel after sitting over night since I did not have the camera but to
my surprise it was still slightly blue and the Liquid Lithium bronze beads on top where still quite noticeable. I attempted to photograph them best as
possible and the thou blueness of it is only present in one of the pictures that shows the brightest blue. The night before It was a bit darker shade
more along the lines of light navy blue.
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
http://www.thevespiary.org/sedit/Private/Pictures/Lithium%20...
PS: When I get the pictures re sized I will embed them into this thread but as it stands there pretty huge and I don't have an image editor since my
computer crashed. Anyone willing to crop them please do and let me know, Thank you.
I am scaling up in a little bit and I will try to document the entire thing for you folks this time and do it 100% right.
Peace and I hope you enjoy the pretty pictures... More to come because this will allow any chemist to perform the powerful birch reduction at room
temperature without the need for Liquid ammonia.
[Edited on 22-12-2009 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Sedit
International Hazard
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Now as far as discussion of this topic goes I would like some feed back please. With little interest in the condensation of Ammonia even though it has
its own forms of potential in organic synthesis. My main goal at the moment is the Lithium Bronze complex AKA Li[NH3]4. This is the substance which is
gaining notoriety for its ability to perform Birch like reductions at elevated temperatures. This is in a much more stable and condensed form of the
common solvat ed Lithium in ammonia system which normally takes on the complex form of Li[NH3]x where x is any number of stable ammonium ion complex.
This Li[NH3]4 system forms a biphasic mixture in a non polar solvent which can be stored at room temperature for several days before it begins to
decompose.
This will allow Birch reductions to be performed at room temperatures in short amount of times without the hazards of gaseous Ammonia which carrys the
risk of suffocation and/or severe chemical burns. I did have a little scare when performing this experiment because the text that lead to this
experiment suggested performing a birch reduction in an atmosphere of NH3 in a balloon. I was a little Leary of doing so because if the balloon pops
it could turn into a bad day which it did manage to do. Only a little pin hole in a balloon that was hardly inflated at all which blasted me in the
face for a split second taking the breath out of me and scaring me more then anything. No harm was done but it emphasizes the dangers that could come
from doing it in a balloon without proper testing of its chemical capabilities. There is also a possibility that I myself was the reason the pin hole
formed but either way care should be taken when handling concentrated ammonia gas.
The main objective of all this work is to synthesis one of the so called Super Bases Lithium Amide with the chemical formula LiNH2. Since the Nitrogen atom is completely unhindered it can act as nucleophile aminating various
alkylhalides to there amines thou an SN2 reaction in high yields If I recall correctly. It has the ability to deprotanate Dimethylsulfoxide when can
then be used as an alkylating reagent. The methylation abilities of LiDMSO is one of my main interest right now. Normal synthesis of this compound
involve the direct combination of its elements by adding Lithium Metal into Liquid ammonia at super chilled temperatures then distilling the Ammonia
to yield the the LiNH2. This bypasses all of this using gaseous Ammonia forming the Lithium ammonia complex which can be decomposed by the formula,
Please correct me if I'm wrong because this seems unreasonable to me.
Li[NH3]4 ---Heat---> Li[NH3]4---> LiNH2 + 3NH3 + H+
Can anyone suggest alternative drying agents instead of wasted Lithium wash bottle. I hear some cause complexes but I can not remember which cause
this.
[Edited on 22-12-2009 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
International Hazard
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Quote: Originally posted by Sedit  | ...
Can anyone suggest alternative drying agents instead of wasted Lithium wash bottle. I hear some cause complexes but I can not remember which cause
this. |
Obviously anything acidic is out, thus no H2SO4 or P2O5/P4O10. Calcium and magnesium salts often form complexes with ammonia, both MgCl2 and CaCl2
will form complexes that volumetrically contain almost as much ammonia as liquid NH3.
NaOH and KOH do well for preliminary drying, CaO can be used to finish the job. If you have ready access to CaO then just it alone; activate it by
heating it to ~700 C for 15 minutes or so.
If the NH3 needs to be really dry, I'd use the lithium drying bottle for a final polish.
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Sedit
International Hazard
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I added an extra layer of NaOH atop the NH4NO3/NaOH mixture which I didn't do the second time(more on that attempt tommorow). I do believe that the
extra layer aids in drying and a whole seperate drying tube with it may be prudent.
CaO sounds like an excellent Idea N_I. I used the middle drying bottle in the first attempt with Lithium grains in Ether because I could not think of
anything else powerful enough and on hand considering last time I attempted MgSO4 as a drying agent in the past, which as you already stated, proved a
huge mistake. When I did it I was getting NH3 exiting out of the system so I did not think much about it till I opened the drying flask that contained
the MgSO4 some two to three weeks later and almost lost my breath to the amount of ammonia it released. I want to try to harness this in the furture
as an ammonia storing system but thats a topic for a whole another thread.
I don't feel I need it really dry because I repeated the experiment just a little bit ago hence the reason im typing this 4:40 in the morning. I just
feed NH3 from the basic generator right into an EtO2/ Lithium suspension and the formation of Lithium bronze formed rather nicely although there where
a few complications and I will get into more detail about them tommorow and show the shitty pictures I took of the whole ordeal.
I want to find a solvate able to extract the Li[NH3]4 Aka lithium bronze without it reacting if such a solvent exist other then liquid ammonia.
Im going to experiment with this just a little bit more as we still have a good amount of snow on the ground but after that I am moving directly on to
the synthesis of Lithium Nitride AkA Li3N which is a strong enough super base to deprotonate H2 itself synthesizing 1mol of Lithium amide and 2 mols
of lithium hydride
thanks again for the suggestions and if anyone else has enything to share feel free. Keepem comming folks because sedits pretty excited over this one
right now
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Sedit
International Hazard
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Attached is a photo of the the midway point or so of the Lithium Ammonia reaction. You can slightly see the tube which is full of pin holes going to
the bottom of the flask. Atop of that is the Lithium Bronze already beginning to form pretty early. I will post more details of the setup later time
permitting but I mush go now.
Keep in mind that this attempt was not as successful as it may first appear due to a number of reasons I will explain later.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Ephoton
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Mood: trying to figure out why I need a dark room retreat when I live in a forest of wattle.
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sedit if the amide is your goal then instead of heating the lithium bronze to obtain it
just add styrene or a simular alkene to the ether mix.
you will then reduce the alkene and precipitate lithium amide with out having to
heat the solution.
e3500 console login: root
bash-2.05#
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Sedit
International Hazard
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My Main goal is to experiment with the stability and reactivity of the Lithium Bronze solution. I have obtained results showing a blue mixture which
goes against what literature appears to state so my main goal at the moment is to figure out why there was a blue solution in the first place.
It appears that the bronze is more stable then I expected it to be. The addition of EtOH to the mixture precipitated a white powder and released a
strong smell of ammonia from the flask.
I have alot more to add but been very busy due to the X-mas and what not so I will be riving this thread as soon as I find the time to post all the
pictures and the write ups I have prepaired.
PS: Can anyone view the pictures posted in my first post? They do not appear to have linked correctly and I can relink them if needed.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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stateofhack
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I can't see them, i think hotlinking them is what is causing the problem
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not_important
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All the image URLs end with "Lithium%20Bronze/..." - something happened to the trailing section including the actual file name.
You might try running them through tinyurl to get a short URL.
If you are running MS Widows, download IrfanView for an image edotor. Free, should handle most if not all your resizing, cropping, contrast and
brightness adjustments, and simple annotation needs just fine.
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Sedit
International Hazard
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Im just downloading Adobe photoshop as we speak so I can edit the size and place them inline like I wanted to. Before they where so large I did not
want to :IMG: them in like I normaly would. Give me a few hours and I will update it all.
Just eliminate the ... at the end of the file and it will take you to the directory to view the files.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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not_important
International Hazard
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Lordy, using Photoshop to resize images is like using a nuclear aircraft carrier to cross a stream. Takes forever to load, eats memory like Microsoft
had coded it; on top of that it likes to phone home to Adobe and leave lots of footprints in files it edits.
Trust me, IrfanView will do what you need with a lot smaller footprint, and is free-as-in-beer. You can even batch process a group of files, say
resizing and changing the file type for them all in a few seconds.
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Sedit
International Hazard
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I know... I know....but its what im use to and since I do a good share of graphical work I try to get the best I can. Since my computer crash I have
so many unexpected issues its unreal because the back up version was corrupted and missed many DLLs and what not. I installed Photoshop and now I keep
getting an svchost.exe - No Disk error blah blah.... ::Sigh:: Either way the more important pictures should be avalible tommorow. Assuming my computer
does not learn how to fly and decide to take a leap out the window......
Should I
A:Cancel
B:Tryagain
Or C: Continue
Im chosing option D at this point which normaly involves a sledge hammer
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Sedit
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Ok so im considering returning to the experiments very soon. Caught up in Xmas New years and my birthday but now I want to review the synthesis and
perform it again on roughly a two gram lithium scale. I have trouble sleeping at night because of the test tube with 1.7 grams of Li thats been in
Et2O since Xmas. If that burst from pressure build up I have a serious issue on my hands and Im not happy about it and would like to make use of it. I
have aired it a few times and it appears to be no longer building pressure but it still disturbs me.
The reason im bringing this up with no experimental data like I normaly would is because I want to get some thoughts on the complexe between Copper
and Ammonia that forms.
If powdered Cu was added here what would happen?
I know it complexes with NH3 but would it do the same in this case? What would be the product? A complexe with Lithium, Copper and Ammonia or what?
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Sedit
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I spent much time making sure everything was on the up and up.
I had my drying tube of NaOH flakes in place, suck back tube in place. Everything was dryed in the Microwave to be sure it was H2O free. I mixxed a
slight excess of NaOH with ammonium nitrate to be sure to add that little extra drying ability. All tubes feed into 1.7 grams of Lithium in Et2O.
It all was well and I checked and double checked to make sure all was sealed and air tight which they where but the problems were yet to come and
rather rapidly at that.
See See it took me about 2 hours to setup and photograph to be sure I went down my checklist of alls well.
Once I was sure it should go correctly I mixed CaCl2 hydrate with Crushed Ice and to my suprize I did manage to quickly get the temperature down to an
easy -35/-40 degrees F i believe(maybe C but in the confusion i forget)
After mixing an amount of ammonium nitrate with an slightly larger then eq molar amount of NaOH I could smell ammonia as expected. This was taking its
good old time till it ran away from the liquid NH3 solution stated below. I had an icebath ready but this proved futile. To initiate such as I normaly
do I drip a few drops of ammonia hydroxide solution to get it ready to go.
Perhaps big mistake..... or just giving a boost to whats gonna happen anyway.
Well withing about 1 minute I started to hear a" loud" fizzing sound proving the NH3 was being created(way to fast at that) but somewhere on the line
it was either pluged or there was to much pressure thru such little lines(doubt it I believe the NaOH drying tube did it). First instinct was to
attempt to cool the reaction vessle to quell the runaway but it was to late and of the seals between the lines busted blastingme in the face with 100%
pure NH3 giving minor chemical burns. I made sure I was ok then quickly got a cup of HCl and placed the leaking tube in it filling the area with
relatively harmless ammonium chloride. This helped alot and I quickly diluted the NH3 generator with excess H2O. I blew HCL fumed across the entire
work area until ammonia chloride stopped presenting itself and made sure to wash completely even thought I keep myself cover almost entirely when
working.
uggg I got alot more to say but il write tommorow.
Peace and be safe
I have pics of the setup but when my hands stop hurting tommorw ill post them.
~Sedit
[Edited on 17-1-2010 by Sedit]
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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Sedit
International Hazard
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Sorry for the double post but since almost no one appears to have interest in a highly useful and reactive alloy between a metal and a gas that gives
a very powerful and even more useful superbase upon decomposition im left to pretty much talk to myself and record my notes here like a good chemist
should. On a brighter note atlest someone heres doing instead of just talking which is a plus right.
Well anyway the reasoning for this post is not to rant but to say that the cause of the seal blow out has been determined and it was exactly what I
thought it was. A prill of NaOH from the drying bottle managed to clog the inlet comming from the Ammonia generator. This is what lead to the quick
catastrophic failure of the tube that connected the drying test tube and the Ammonia generator. When it popped off it turned right towards me like a
high presure fire hose would have and I had to quickly grab it to avoid being completely overwhelmed with NH3 gas. In the process I suffered very
minor chemical burns on my right hand but nothing more then a bit of redness on my hand(And I almost ALWAYS where gloves of some kind but my Ego
got in the way this time and I didn't see the need Save the scolding for someone
that doesn't know better). As stated the tube was quickly lead into a small vessle of Muratic I had on hand right there just for this sort of
thing so I guess being a boy scout and the always be prepaired motto paid off for a change eh.
Well Im going to revamp my drying tube and possibly attempt to reproduce this experiment tonight since the Lithium vial was open and surely more
decomposition is to be expected although after stoppering the vial there was no pressure build up so thats a very good sign showing that H2 was not
being produced due to decomposition. The fact that its Sunday and I may not be able to find time to perform it tonight since I have to get up early
and perform most of my work at night when the young budding chemist are all asleep.
:Sigh:
I would like some kind of feed back here folks even if its to tell me im a complete idiot. If not I will more then happily take my research elseware.
But I can almost assure you that aside from the synthesis of the Lithium ammonia complexe that there is some form of contamination that can solvate
the electron in ether.
This effect has already been noted in various ethers as it stands at extremly low temperatures so the idea of finding something to promote this effect
at relativly higher temperatures is noteworthy indeed if not publishable if you ask me.
Also I would like to know Ethers aside what Non reactive non polar solvent has the highest solubility for NH3.
Thanks for your time for those that felt the need to show some interest!
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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watson.fawkes
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Sedit, I can affirm that you are a good person.
Also, I am reading this thread with interest but nothing to say.
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aonomus
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I'm also reading this thread with interest, but I don't really have anything to add or comment on. This is something that is interesting, but I can't
replicate it myself, nor contribute, so I can only cheer from the sidelines. Keep at it Sedit
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Sedit
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thanks for the support guys. Anonmus trust me if I can do it you can do it.
There is no doubt in my mind about that. I am just now getting prepaired for another take at it and I made a new drying bottle clog proof and in about
10 minutes alls a go.
Honestly the drying bottle is "useless" other then increasing yeilds because H2O turns to Hydrogen and LiOH while the rest of the lithium
complexeswith the Ammonia.
Now can someone please explain to me the REAL structure of this compound? Is there a delocalized electron in there somewhere thats screwing with my
attempts to draw this structure? They state Li(NH3)4 but this makes little sence to my chemicaly declined mind.
When Im finished this I will attack many other complexes with NH3 just out of curiousity. Copper seems like it could be interesting honestly.
Anyway I will try to report and post pictures tommorow but as many know my computer is crap and just getting pictures posted and resized is a PITA so
we will see. When all gets worked outI will have a mess load of eye candy for you folks.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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aonomus
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Well its not so much the resources/chemicals, but the location. From the way you describe it, you went outdoors and did it on a porch or something. I
live in a dense townhouse block with no completely fenced in backyard. Someone taking their dog for a walk could make my life complicated to say the
least.
I'll see if I can look up some references for you Sedit over my lunch break, perhaps something in the literature can indicate what the Li(NH3)n
complex is.
Also, its already known that Cu*(NH3)n complexes exist, probably a few videos on youtube. I would maybe like to see fine powdered Cu attacked by
gaseous NH3 out of curiosity.
You could probably go
CuSO4 + Na2CO3 -> CuCO3 -heat-> CuO
CuO + C -heat-> Cu(s)
Although one tip I might have for you, take a trip to the pet store and look for plastic airstones, they should be resistant enough to solid
NaOH prills, and could solve the clogging/exploding/owowhand problem for you.
Oh, and you can do [ i m g=WxH ] url [ / i m g ], but it only resizes in the browser, so the people viewing the thread still download all that data.
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Sedit
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Give me tommorow and you will see it all. I will update some pictures and inline them.
I just reproduced but got some of the strangest results yet.
No blue color.... No clear with Gold biphasic mixture,.......
Brown and I have no idea why the hell the Et2O turned brown. All im left to
assume is that its some sort of colloide with the Lithium bronze or someshit.
Ill let you see the pictures tommorow and see if we can make sence of them.
Gotta run tired and in a hurry.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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watson.fawkes
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Li(NH3)4 is an excellent lesson on why chemistry is applied quantum mechanics. The standard rules are not fundamentally true in any way, but represent
approximations of the standard central-force solutions to the Schrodinger equation. Sometimes the full picture doesn't follow those standard rules.
This article on the compound in question
A Molecular Perspective on Lithium-Ammonia Solutions has full text available at that link. It's a review paper and is more readable than a
research paper. Here's the abstract. (Some formatting errors are present.)
| Quote: | | A detailed molecular orbital (MO) analysis of the structure and electronic properties of the great variety of species in lithium-ammonia solutions is
provided. In the odd-electron, doublet states we have considered: e-@(NH3)n (the solvated electron, likely to be a dynamic ensemble of molecules), the
Li(NH3)4 monomer, and the [Li(NH3)4+ e-@(NH3)n] ion-pairs, the Li 2s electron enters a diffuse orbital built up largely from the lowest unoccupied
MOs of the ammonia molecules. The singly occupied MOs are bonding between the hydrogen atoms; we call this stabilizing interaction HH bonding. In
e-@(NH3)n the odd electron is not located in the center of the cavities formed by the ammonia molecules. Possible species with two or more weakly
interacting electrons also exhibit HH bonding. For these, we find that the singlet (S=0) states are slightly lower in energy than those with unpaired
(S=1, 2) spins. TD-DFT calculations on various ion-pairs show that the three most intense electronic excitations arise from the transition between the
SOMO (of s pseudosymmetry) into the lowest lying p-like levels. The optical absorption spectra are relatively metal-independent, and account for the
absorption tail which extends into the visible. This is the source of Sir Humphry Davys fine blue colour first observed just over 200 years ago.
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Sedit
International Hazard
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Sorry if its a little large I am having a bitch of a time with this computer and did manage to get one decent picture resized so show whats going on.
This is completely different results then I had before and the only thing I can think of is that it has something to do with the fact that the Lithium
has been sitting in the Et2O since Christmas
This is the very early into it and next to no Lithium bronze has started forming yet although if you look very closely you will see very small specks
of it in there that sort of resemble bubbles
This morning I woke up to find the Ether is a greenish color with all sorts of precipitate and unreacted Lithium out the wahzoo. I had major issues
with the NH3 generator which highly complicated things to say the lest keeping me up until about 6 in the morning which is something im not happy
about working around this stuff while half asleep.
Im going to hunt down the Kipp generator I made sometime back and use that from now on since that should be able to give me the nice steady supply of
Ammonia I need for the experiment. I did manage to get a good amount of the bronze complex and if I can find out WTF I did with my camera 6 in the
morning I will take pictures and post so that you all can see the now Green Ether.
I will post more later but its early and the kids are off school so I have a mess load of chours to do(God I sound like a woman).
PS: I also did away with the drying tube which I think I forgot to mention before I believe. So as it stands you DO NOT need to dry the ammonia to
form this complex.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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watson.fawkes
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| Quote: Originally posted by Sedit | | Now can someone please explain to me the REAL structure of this compound? Is there a delocalized electron in there somewhere thats screwing with my
attempts to draw this structure? |
When I posted the review paper above, I had only scanned it briefly. The
answer to your question, specifically, is yes. It's described in section 5.1. "The Singly Occupied Molecular Orbital (SOMO)". That's where your
electron went. There's a density diagram for it. It's somewhat like a Rydberg state (high principal quantum number around a center), but with a
deformation where the electron density is concentrated around the four triangular faces of a cuboctahedron, each face corresponding to an ammonia
unit.
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Sedit
International Hazard
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LOL thanks for the responce watson i mean it.... but its late and ill have to get back to you on that one tommorow because there was so many big
words in there.
I kind of get the point though ust a bit confused.
Knowledge is useless to useless people...
"I see a lot of patterns in our behavior as a nation that parallel a lot of other historical processes. The fall of Rome, the fall of Germany — the
fall of the ruling country, the people who think they can do whatever they want without anybody else's consent. I've seen this story
before."~Maynard James Keenan
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watson.fawkes
International Hazard
Posts: 2793
Registered: 16-8-2008
Member Is Offline
Mood: No Mood
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| Quote: Originally posted by Sedit | | [...] because there was so many big words in there. [...] I kind of get the
point though ust a bit confused. |
You think you're confused now, just wait to you get to the article. I'd
highly recommend reading it, even if it takes you a month or two plow through it while you learn the background material. It's the most direct way to
getting smarter I know of.
Apropos the biphasic mixture of blue solution with bronze solution on top, it only occurs at lithium concentrations and temperatures. There's a phase
diagram in the paper you'll find useful in that regard.
Plus, I didn't know that the lithium bronze solution isn't just metallic-looking, it's a proper liquid metallic phase! And, if that weren't enough,
it's a better electrical conductor than mercury. That paper is full of great stuff, such as a computation of the density of solvated free electrons
(they become part of the solvating cage, more or less), interesting discussions about the transition to metallic state (TMS) (a phase transition
that's just not all that common), a novel kind of H-H bond (not the typical hydrogen bond, but enough to stabilize complexes).
It's also yielded the first real insight I've ever had about the quantum origin of the liquid phase. They do computations for coupled radicals,
starting with the dimer. The dimer has a number of geometric configurations which are all very slightly exothermic, a little over an eV/molecule,
which is down at thermal energies, and which differ from each other by about an order of magnitude less. So one can pretty easily imagine how the
liquid phase arises when bonding can happen promiscuously upon collision, given the high geometric density of permissible configurations, and yet also
break because of fluctuations from thermal motion.
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