Sciencemadness Discussion Board

lithium citrate or lithium hydroxide?

ManyInterests - 31-3-2022 at 09:54

I ordered from lithium chloride online a few weeks ago, this is because I wan to give Laboratory of Liptakov's LL8 a go, but it got me curious as to how I can synthesize my own lithium chloride in the future. I read on wikipedia that lithium chloride can be made by treating lithium carbonate with hydrochloric acid. Lithium carbonate can also be made by mixing lithium citrate with sodium carbonate.

Only problem is, I don't know where I can get lithium citrate. I did read that lithium hydroxide is replacing lithium citrate. I know the citrate is an acid while like the hydroxide is a base, but can lithium carbonate be made with lithium hydroxide?

I found nothing on how lithium citrate can be synthesized? I know that lithium metal can be extracted from lithium batteries (nurdrage and many other youtubers have videos on it. It is an elementary process, and much cleaner than getting manganese dioxide!). If it can be synthesized, I would like to know.

Anyone got any information on it?

[Edited on 31-3-2022 by ManyInterests]

clearly_not_atara - 31-3-2022 at 11:48

You don't know where to get lithium this, but maybe you can make it from lithium that. But now you don't know where to get lithium that?

Here's an idea: find out which lithium compound you can obtain, if any. Then we can figure out what you can make from it!

EDIT: to make Li2CO3 from Li metal just add it to a warm solution of NaHCO3. You may need to stir. Be careful about the heat of reaction.

[Edited on 31-3-2022 by clearly_not_atara]

ManyInterests - 31-3-2022 at 12:33

Hmm, this is strange. I thought I posted a reply here with another link I found. I guess I'll have to write it again.

So I found this link:

https://www.drugs.com/pro/lithium-citrate-syrup.html
Quote:
Lithium citrate is prepared in solution from lithium hydroxide and citric acid in a ratio approximately dilithium citrate.


Apparently lithium citrate is prepared by adding lithium hydroxide and citric acid in solution. I don't know what the ratio of dilithium citrate is, but I guess with that little discovery I will need to experiment (and properly document) with various proportions and see what happens.

So far from what I see it the process to get lithium chloride will require the following ingredients.

Lithium metal (easily obtained from lithium AA batteries)
Citric acid (I know a few grocery store that sell that, I got some already)
Hydrochloric acid (I got some pure 31.5% and it's easily available from most hardware stores near me)
Sodium carbonate (which I already have, and is easily prepared by putting baking powder in the oven at 230 degrees Celsius for a few hours).
Distilled water (finding this one will be a true challenge!).

Steps so far in my mind is to add the metal to the water to make the lithium hydroxide, then from there mix it with citric acid to make the lithium citrate, then with the sodium carbonate solution and finally with hydrochloric acid.

When I start on this I will document everything and report my progress here.

[Edited on 31-3-2022 by ManyInterests]

j_sum1 - 31-3-2022 at 14:16

You want LiCl2? You have access to Li metal? It would seem to be a straightforward process.
React Li metal with water. Go slow.
Neutralise with HCl.
Evaporate.
Recrystallise to purify.

I am not seeing a problem here.

[Edit]
Or you could go via the carbonate. Li2CO3 is remarkably insoluble. So, adding carbonate to pretty much any lithium solution will give a precipitate. Once you have Li2CO3 then react with the appropriate acid to give the desired salt.
Again, I am not seeing a problem here.

[Edited on 31-3-2022 by j_sum1]

Texium - 31-3-2022 at 15:45

Quote: Originally posted by ManyInterests  
Steps so far in my mind is to add the metal to the water to make the lithium hydroxide, then from there mix it with citric acid to make the lithium citrate, then with the sodium carbonate solution and finally with hydrochloric acid.
Too many steps for what should be a much simpler process (as j_sum1 outlined). It makes it clear that you don't really understand the chemistry going on here. There is no point in making the citrate as an intermediate when you can make the chloride directly from the hydroxide and HCl...

Something else worth noting is that LiCl is extremely hygroscopic. You will not have an easy time isolating it as a solid, as even on boiling down a solution of it you tend to be left with a syrupy liquid.

j_sum1 - 31-3-2022 at 18:39

Quote: Originally posted by Texium  

Something else worth noting is that LiCl is extremely hygroscopic. You will not have an easy time isolating it as a solid, as even on boiling down a solution of it you tend to be left with a syrupy liquid.

Good point. Most of the time I have made LiCl I have just needed a small quantity of solution and so have not needed to bother with this annoying detail.

ManyInterests - 31-3-2022 at 18:41

Quote:
Too many steps for what should be a much simpler process (as j_sum1 outlined). It makes it clear that you don't really understand the chemistry going on here. There is no point in making the citrate as an intermediate when you can make the chloride directly from the hydroxide and HCl...

Something else worth noting is that LiCl is extremely hygroscopic. You will not have an easy time isolating it as a solid, as even on boiling down a solution of it you tend to be left with a syrupy liquid.


Quote:
You want LiCl2? You have access to Li metal? It would seem to be a straightforward process.
React Li metal with water. Go slow.
Neutralise with HCl.
Evaporate.
Recrystallise to purify.

I am not seeing a problem here.

[Edit]
Or you could go via the carbonate. Li2CO3 is remarkably insoluble. So, adding carbonate to pretty much any lithium solution will give a precipitate. Once you have Li2CO3 then react with the appropriate acid to give the desired salt.
Again, I am not seeing a problem here


Yeah I always overcomplicate things. I had no idea I didn't need to go through the citric acid route. If just adding lithium to water and then using HCl.

I might do it in different ways just for fun and see what results I could get. In the end of the day buying lithium chloride is obviously the best route since it's purity guaranteed and isn't that expensive. But I like to have the knowhow to make my own reagents.

And J_sum1, are lithium batteries restricted where you live? Where I live there are lithium batteries of all sorts (mostly camera batteries, although there are plenty of places that sell energizer AA and AAA lithium batteries). The only downside is that they are quite pricey. A pack of 8 AA batteries is like half the price of the 100 grams of lithium chloride I bought.

j_sum1 - 31-3-2022 at 20:48

I can buy AA and AAA lithium batteries quite easily but yes, they are bit expensive. They are still a pretty convenient source of lithium if you need it. I have always found I get a bit of contamination from the other components of the battery but it has not been a problem.

Most other lithium batteries that I come across are rechargeable lithium ion batteries. I began a project to recover the lithium from these, but abandoned it because (a) it is really messy and (b) it is a royal PITA to crack open those steel casings. The route here is dissolve in acid, filter, precipitate with carbonate and filter again. Then do as you wish with the lithium carbonate. Like others who have tried this, I have found the yield low -- I am not quite sure where the lithium has gone to, but I have recovered a lot less than what is theoretically in the batteries.


For me personally, I now have little need to crack open the batteries. I have 250g of lithium rod (which has a thick nitride crust but is otherwise ok.) I also have a couple of 50g packets of properly stored lithium for if I need high purity.

ManyInterests - 1-4-2022 at 04:09

I didn't think of outright buying lithium metal! I mean I still have a lot of (very pure) nickel strips for NHN synthesis and any other nickel compound I might need.

ManyInterests - 8-4-2022 at 20:13

http://www.chlorates.exrockets.com/lithium.html

I looked up over there that it seems I was going through too many steps! It appears that the only thing I need to make lithium perchlorate is lithium hydroxide (easily obtained by adding lithium metal to water) and ammonium perchlorate. I am guessing my current challenge is to make ammonium perchlorate, which is something I was planning on doing anyway.

I will also need to get a platinium anode to convert my current supply of lithium chloride into lithium perchlorate, that seems to be the easiest route as far as I see it.

EDIT:

http://www.chlorates.exrockets.com/litpat.html

I find this part very interesting:
Quote:
To initiate the electrolysis, the aqueous solution is introduced into an electrolytic cell between an anode and a cathode. Although various types of oxidation-resistant anodes, such as platinum, graphite, or lead dioxide, may be employed in the cell, platinum has been found to yield the best results, especially when used in conjunction with stainless steel cathodes.


The patent basically is saying that they can go directly from lithium chloride (which I have) directly to lithium perchlorate, which is very good given how ridiculously soluble lithium chlorate is (it is probably more soluble than the chloride!)

While they did say that a platinum anode was found to be the best, platinum anodes are very pricey, and if they were able to get results with something else, like an MMO anode.

They did mention graphite, which I have plenty of from batteries, but don't want to use because I don't want to contaminate my product when they inevitably start falling apart.

Since I have an MMO anode, I wonder if it'll work in conjunction with my titanium cathode.

[Edited on 9-4-2022 by ManyInterests]