chief
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LiAlH4 synthesis
Just to proove how cheaply it can be produced, here the synthesis, as from "Brauer"; I didn't try it myself, but probably someone will ..
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Attachment: LiAlH4.pdf (184kB)
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DJF90
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[sarcasm] Oh yes I see, its the massively easy, massively cheap synthesis of LAH, from readily available starting materials! [/sarcasm] On a more
serious note, you STILL seem to be missing the point! I agree its simple, IF you have access to the required chemicals. Most don't. And if they do,
theres two likely scenarios. The first is that they also have access to LAH, the second is that they dont want to waste 3 eq. of lithium hydride,
seeing as lithium is expensive and the hydrogenation process is less than friendly.
Seeing as YOU seem to think its possible to make a kilo for about $20, why don't YOU prove it, and put us all to shame. Something tells me you're
living in cuckoo land though. Looking simple on paper and being simple practically is FAR from realistic.
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chief
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Yeah: Maybe I look up those 500 gr. of Li-citrate which I have in the basement since ages ... and start it ... 
So you poor guys don't have any LiH ?? Noone gave it to you ? 
Why not just make some:
Attachment: LiH.pdf (80kB)
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DJF90
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Again, you've missed the point. Lithium is hard to get in quantity, even by electrolysis, and you're still wasting 3eq. of it (via the hydride).
Even if you consider non-aqueous electrolysis instead of fusion of the salt you're still going to have a hard time. What I'm saying is that, no, its
not hard to make LAH, its just difficult on the scale you propose (or even anything more than say 0.5 mole). Plus many will shun away from the
possibility of an explosive atmosphere with the H2.
And we're quite capable of refering to Brauer, theres a copy in the forum library, although there are other sources of practical information for
preparation of inorganic materials.
[Edited on 11-5-2010 by DJF90]
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chief
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Sorry, man: I appreciate your posts, usually, but this here is the synthesis-thread ..., !
Besides there are videos on youtube of how to plainly extract elemental Li as foil from photo-batteries ...: Thereby Li is obtainable in the shop
around the corner ..., in 90% of the world ... ; shall we have another thread on this ? Li from batteries ?
==> A melt-electrolysis-setup may be somewhat demanding, but surely can be done ...; old Li-accus or batteries can be found in a lot of places too
...; Li is _everywhere_ ..., once you start looking ...
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stoichiometric_steve
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chief, you're so amazing, proving us all wrong. But why don't you go out and get a girlfriend? This, i suppose, would solve your issues.
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a_bab
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Unless you sell me LiAlH4 with under 50 bucks/kilo no matter what you're saying is just speculation.
I agree one can make rather easily let's say 10 grams of it, but for a larger amout, there are lots of issues, one being the fact that it reality it
takes HOURS to have the LiH produced. And don't forget the Li batteries - I'm under the impression you'd get under 1 gram of Li from one, so it get's
very expensive.
I do wish you success isolating the Li in kilo amouts out of your cheap, pottery grade lithium carbonate though.
I don't agree with the price SS asks for LiAlH4, but I don't need the stuff either. Actually I'm totally against selling such things on the Internet
to unknown people, without having a legitimate business. Because the truth is, 90% of the members here are home scientists (clandestine chemists in
the eyes of the big bro).
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DJF90
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If you're trying to say I'm oblivious to OTC sources of Lithium you're completely wrong. Extraction from batteries has been documented all over the
web. But you're STILL missing the point; For the scale you proposed in Steve's thread (i.e. 1kg) for the price you've proposed (i.e. <$20 if I
added it up right) its just NOT possible, especially as you're now suggesting extraction of lithium from batteries as opposed to raw material (i.e.
electrolysis of the chloride, with some KCl added for lowering of the melting point IIRC). Electrolysis to obtain the metal may be doable, but it
presents much larger hurdles than that of sodium extraction (Len1 presented a beautiful article in Prepublications), and so its not a particularly
viable option for a large number of members here.
However, even if you do succeed, its energy intensive, especially as conversion to the hydride in a subsequent step also requires 550C and hydrogen
atmosphere, all in all, a potentially explosive situation. If by some miracle you do manage to make the ~800g Lithium hydide needed (think about
volume of the apparatus here!), then 3/4 of your hard work goes to waste in order to make that elusive kilogram of LAH. I'm not even going to start on
the preparation of AlCl3, another unobtainium for many here.
I don't want to put a downer on this, but its an unrealistic challenge for many. Get it to work though, and you'll be a king (so long as you post it
here (with pictures!) of course).
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psychokinetic
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If you made a tonne, then maybe each kg would be made for ~$20, but one singly kilogram is pushing it, methinks.
Still, I'd be interested to see it happen.
“If Edison had a needle to find in a haystack, he would proceed at once with the diligence of the bee to examine straw after straw until he found
the object of his search.
I was a sorry witness of such doings, knowing that a little theory and calculation would have saved him ninety per cent of his labor.”
-Tesla
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Chainhit222
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last time I tried to buy a girlfriend I had to fill out DEA order forms
The practice of storing bottles of milk or beer in laboratory refrigerators is to be strongly condemned encouraged
-Vogels Textbook of Practical Organic Chemistry
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grndpndr
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Yup methinks a chick and some sooothing dowtimes needed
$20 kilo thats a pretty inexpensive girlfriend unless your 14
Do yo'all know crank can cause crankiness,paranoia,dementia?
Not to mention after a year or so using you can forget even a $20
per hundredwieght chick due to serious health problems.Black teeth
body sores etc etc.
Particularly in the underdevoloped young mind/body,not saying its a healthy
choice for us dementia demonized,forgetful,dorky elderly folk who dont know shit from shinola except in thier depends.
Good luck with the inexpensive lithium and 'chemistry' my young friend!?
[Edited on 12-5-2010 by grndpndr]
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woelen
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I think that chief refers to an alternate universe with alternate elements in which they rearrange into the right reagents just by magic and a little
cookery. But now let's get back to real-life and not some funny fantasy movie
I have done quite a few syntheses of different chemicals (e.g. KBrO3, KIO3, KIO4, Na2TeO3, Na2MoO4, CsICl4) and with all of these synths I came across
all kinds of practical problems and with some of these chemicals I had to try a second or even third time before I really had satisfactory results.
Even something simple like making and isolating pure and high grade BaCl2 from pottery grade BaCO3 and dilute HCl in good yield has proven to be much
more troublesome than I initially imagined. And all of these chemicals are not even the most difficult ones, no special atmosphere needed, no high
temperatures involved, etc.). Making _and isolating_ chemicals mostly is a challenge from an engineering point of view, not from a chemical point of
view. And this is where most of us have the biggest trouble. Let's be realistic: there are so few members who really solved the big engineering
challenges (e.g. garage chemist, len1) of making the more reactive stuff like Na and SO3.
So, even if you can get your Li2CO3 for free and other stuff like HCl, KCl and whatever other OTC reagents you may need, then still you won't be able
to make LiAlH4 from simple materials around the house without a lot of effort and probably a lot of cost (constructing the apparatus for making e.g.
Li also must be taken into account). Chief, I invite you to come up with a list of items you think which are needed to make LiAlH4. I am thinking of
things like H2-generator, drying apparatus, high-temperature electrolysis apparatus and probably much more. Just try to give a summary of all things
you need and then think over the entire process.
So, I think that some members over here might be able to make LiAlH4 from easy to obtain basic chemicals, but those members will be few, very few, and
I am not one of them.
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chief
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Yeah, that's the difference between vchemistry and cooking ... : I did refer to chemistry ...
Let's have the LiH and the AlCl3 first:
LiH ::
==> Have some quartz-glass-tube, or maybe even vessel, and blow the hydrogen throught the Li-melt, as decscribed in the pdf above ... ; of course
either you have some electric furnace or need to construct one ... : 600-700 [Cels] is still easy ...
==> The H-stream would be let flow before any heat gets started to avoid explosions... : Either have a bottle, or a electrolysis-cell
(stainless-steel electrodes and NaCO3-sol. as electrolyte) or maybe even use the acid-metal or Al-NaOH- method while making some other useful chemical
...
==> I personally would get the H from a bottle or a electrolysis-cell ...
==> Who has no furnace may have to construct one ...
=====================
AlCl3 ::
==> still have the furnace ? fine ... !
==> Using the clean Al from electric cabling: Melt it to 700 or 800 [Cels] and blow Cl through it ...
=====================
Anyone but a cook can get this so far done straight-forwardly ..., may be needed some intial experiences with constructing furnaces or handling
quartz-glass first (which me mineralogist just has ... ) ...
========================
The you distill the ether: No peroxide-danger will be tolerated, and always fresh ether will be made ...
List of parts so far: 1 furnace, maybe 1 controller, some quartz-glass and some gas-generating for the H2 and Cl2 ...
==> If you have the HCl as cheap as I have (cheaper than beer) both gases are no big deal ...
========================
========================
Obviously you will definately want some N2-bottle for the inert atmosphere, Ar might be a choice too ...
==> Not much of it is needed ...
========================
========================
Of course once you have the details mentioned here the road is free for the production of hundereds of kg of the hydride ...
==> Any company, which does it, makes it by the tons, which means the cost of production ist below 20$/kg .
I though did not say "steve" or whoever could make it that cheaply ...
=============================
=============================
Now: Could the AlCl3 be shipped legally ? The LiH ? Anyone want some ?
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not_important
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Quote: Originally posted by chief  |
AlCl3 ::
==> still have the furnace ? fine ... !
==> Using the clean Al from electric cabling: Melt it to 700 or 800 [Cels] and blow Cl through it ...
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Way overkill, too much effort for that. Heat aluminium turnings o 250-300 C and pass dry HCl or Cl2 over them. The reaction is exothermic, especially
with Cl2, so only a slow of gas unless you want thrills. The temperature is low enough, unless you get carried away, that borosilicate glass can be
used, this is much easier than finding something that will stand up to Cl2 at 700 C.
Moisture and oxygen lead to the formation of basic chlorides, resublimation can be used to purify it.
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DJF90
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Even easier would be the reaction with bromine, as the aluminium bromide will also undergo the reaction with LiH. But again, processes on the scale
discussed by the OP are unrealistic for the amateur.
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Jor
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I think the most practical and safe way for the amateur is putting the Al foil or powder in some dichloromethane, and adding the bromine slowly. The
DCM dilutes the bromine and prevents a very vigorous reaction. You may need to clean the Al with some HCl however, or the reaction may be slow because
of the oxidation layer (or add a trace of Hg). This way you avoid high temperatures. After the reaction evaporate the DCM. I have used this method to
make metal halides like anhydrous CuBr2 and SnI4.
But from an enironmental point of view, I think the reaction of anhydrous HCl with Al metal at high temperatures is the way to go.
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Fleaker
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Frankly, I'm not a big fan of LAH. Sure, it does some convenient things, but I'd rather go with catalysis any day...
I hate working with it. I've never had a fire with it, I just hate the damn workup.
Anyway, once upon a time I would've been in a position to try this reaction out. No longer. If one can get the lithium, then the rest of the procedure
is *relatively* easily accomplished with a tube furnace. It's getting lithium in quantity that is difficult. I wonder how many people here can say
they have ever dealt with liquid lithium? Evidently not Chief, if he thinks he will make LiH in a quartz or borosilicate tube. Lithium is a great
solvent for quartz, trust me  In fact, 'tis a great solvent for many things when
in vapor or hot enough a liquid! Methinks you best handle it in iron.
I'd go with AlBr3. More easily prepped, and Brauer claims that someone claims that the chemistry is easier
Neither flask nor beaker.
"Kid, you don't even know just what you don't know. "
--The Dark Lord Sauron
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chief
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No: Of course Li is not directly to be handled in any glass; I frankly would have to look the right material up, but would bet on stainless steel ...
That's why I posted the procedure above, see the pdf: Inside the quartz-tube is a inlet of iron ... ...
==> Anyhow the quartz-tube might not even be necessary at all, seen this way: That makes the entire setup ay more simple, since stainless-steel-
vessels are widely available ... and can easily be put under inert atmosphere ...
Though I still have to research the right material for the Li-electrolysis-cell: I bet on stainless steel again, from my experiences with NaOH- and
Na2CO3-melt at 800 [Cels] ...
Before I attempt the Li I'm gonna test it with making Na ... from NaOH-melt ..., since I have lot's of NaOH around ...
==> My only problem here: What _isolating_ material will withstand the NaOH-melt at 330 [Cels] for a length of time ? The isolator is needed for
collecting the Na under it, having the Kathode below it ...
==> Can pyrex hold up to NaOH at 330 [Cels] ? I wouldn't bet on it ...; any other acidic material will not go too far either ...; but then again
it's _only_ in the 300s ...
[Edited on 13-5-2010 by chief]
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Panache
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| Quote: Originally posted by chief |
==> My only problem here: What _isolating_ material will withstand the NaOH-melt at 330 [Cels] for a length of time ? |
Gold, costs about $75/kg, platinum would also suffice and cheaper at $12.50/kg
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chief
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Of course the speach is about _electrically_ isolating material ...
==> Have you ever heard about how alkali-metals are made ? No ??
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Formatik
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| Quote: Originally posted by chief | | Just to proove how cheaply it can be produced, here the synthesis, as from "Brauer"; I didn't try it myself, but probably someone will ..
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It's good to share ideas, but if you expect someone else to try your propositions, more often than not, nobody ever will.
There is another preparation thread on LiAlH4: http://www.sciencemadness.org/talk/viewthread.php?tid=12022
English version of Brauer is in the forum library with those same syntheses.
For the hydrides, with the patent (below) sodium hydride is made from introducing H2 into sodium heated in paraffin oil at atmospheric pressure,
different than the vacuum tube method given in Brauer.
Attachment: US3116112.pdf (96kB)
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Ephoton
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this is something I would truly love to master one day.
I hope you notice cheif that I say oneday having played a bit with lithium I think you will find the
stuff quite scarey. I know I have.
I wonder though if one was to heat an azide in an atmosphere of hydrogen would it make the hydride
a little easier to obtain.
I know that pure alkali metals can be made this way so maby the hydrides can as well.
I know sedit was working on a way to lithium nitride which is easily made into hydride.
this required high stirring speeds at around 200 C or so in an oil with nitrogen pumped into the oil and the
lithium being stirred to a very fine particle size under the oil.
I had quite a few arguments against this as people think that the particle size must be very small.
but the thought that comes to my mind is how to make potassium mercuric iodide. this is done with
KI/I2 solution and is just stirred at RT with some mercury in it.
if its possible to do this on a mag stirrer in a reasonable time I can not see why an element that is much
lighter than mercury should not be as easily reacted when it is more reactive than mercury.
e3500 console login: root
bash-2.05#
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Sedit
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| Quote: | I know sedit was working on a way to lithium nitride which is easily made into hydride.
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Nope, Just the LiNH2 for the time being. Got all the needed materials but lack the time needed to work out the reaction safely. Something about
working with heated hydrogen gives me the willys and I want to make sure I have the time to do it right.
N2 is avalible dry in containers and the reaction seems pretty straight forward though. React Lithium with N2 in a heated tube then H2 is passed over
this at a later stage forming LiNH2 and LiH. Two useful products but I have no idea how one would seperate them at the moment other then the
posibility of performing the reaction in a media whos density lies between that of 0.82 g/cm3 - 1.178 g/cm3, LiH and LiNH2 respectively. This should
allow the LiH to rise atop the fluid and LiNH2 to sink to the bottom.
| Quote: | I had quite a few arguments against this as people think that the particle size must be very small.
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Smaller the better but I don't feel that it is 100% needed to produce the nitride from the method your speaking of. They used Melted Li in that
process and I find it hard to think that it would have trouble reacting in that state needing some high speed stirring to whip it into a fine size
like the suggest. What would happen if it wasn't super fine? Possibly the nitride encases the Lithium... still does not seem like a reasonable concern
and if anything just would increase reaction time. Given that patents like to sell things on an industial scale time would be a factor. In a home
setting allowing a small reaction to run for an extra hour, which would possibly equate to days on a huge scale, is just not an issue.
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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the whole idea got me very excited when I first read of your intentions.
truly alkali amides and hydrides are very usefull indeed.
I would be super carefull as well working with high temps hydrogen and lithium compounds.
still I lack the place to do such experiments so I am stuck watching in awe as others pull of what
has been thought as impossible to the amature in the past.
e3500 console login: root
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