Sciencemadness Discussion Board

Lithium and Sodium

MR AZIDE - 17-6-2012 at 10:33


Would It be OK to store Lithium and sodium metal, in WD-40.?

I cannot find mineral oil anywhere, so I figured WD-40 would be stable.

I ask this before I spend a few Quid on busting open Ultimate Lithium batteries, and before I have another go at electrolyzing Na out of molten NAOH. ( albeit very small amounts)

( I found that Na will even react with cooking oil, to form a white, slimy coating)

Edit.....What about storing Li, Na in white spirits??, which appears according to MSDS sheets is Naphta, / petroleum

[Edited on 17-6-2012 by MR AZIDE]

Endimion17 - 17-6-2012 at 10:46

Kerosene is a worldwide staple for storing sodium.

WD-40 would be OK, but I've just read that the propellant gas isn't butane anymore, but carbon dioxide, which would make a crust on alkali metal surfaces.

I'd suggest you to open your lithium batteries shortly before using lithium. They contain lithium in the form of a foil which is prone to oxidation and crumbling to waste. The only wy to somewhat prevent this is to pack the foil in a small, airtight bottle with as much kerosene/oil as possible, to limit the amount of air above it.

inspector071 - 17-6-2012 at 10:47

Do pharmacies in the UK not carry mineral oil as a laxative? They come in 350 mL or so bottles over here in the US.

MR AZIDE - 17-6-2012 at 11:01


Thanks for the info on the WD-40, Endimion17.!!

When I managed to isolate some small bits of sodium, I had these in the WD-40, and could see tiny trains of bubbles releasing from the liquid.
I naturally thought that this was the Na reacting and releasing H2, but now I realise it was more likely acting as a little nucleating site, and releasing the CO2 contained in the liquid.

I have some 'FLAT' WD-40 in a can thats about 10 years old, Ill need to drill a hole in the side of the can to get the WD-40 out, considering its age it may contain no CO2



[Edited on 17-6-2012 by MR AZIDE]

vmelkon - 17-6-2012 at 11:19

Why don't you just put it in a glass tube and weld it shut? (if you are looking for a long term storage)

blogfast25 - 17-6-2012 at 12:15

Quote: Originally posted by inspector071  
Do pharmacies in the UK not carry mineral oil as a laxative? They come in 350 mL or so bottles over here in the US.


Dunno but hardware stores in the UK definitely stock clear kerosene (lamp oil).

m1tanker78 - 17-6-2012 at 15:08

The 'bubble train' is observed even when you dunk sodium into freshly opened mineral oil. It helps if you heat the MO before hand in a metal container until it stops frothing. The down side is that this tends to tint the oil but it settles out after several days.

If you're interested, here is a thread that's dedicated to cleaning alkali metals although it's mostly aimed at sodium.

I'd stick to MO or kerosene. Look in the laxatives section of a few pharmacies and you're bound to find it. Many here swear by kerosene but I can't personally vouch. Mineral oil has worked great for me. Toluene is next but oh that flammability.. :(

Tank

Mineral Oil

theobromacacao - 18-6-2012 at 05:29

I've always used Liquid Paraffin (250ml amber bottles) from UK pharmacies such as Boots, and it's been fine for Li and Na storage. Quite cheap too!

DerAlte - 18-6-2012 at 20:03

I have often wondered how suppliers of Li metal pack and ship the stuff. Li is so light that any hydrocarbon (SG ~0.89) causes it (SG ~ 0.59) to float largely out of the liquid. Perhaps some of our professional chemists that use the stuff can tell us.

My personal experience with a strip extracted from a battery several years ago is that it begins to oxidize immediately, probably to hydroxide due to humidity. This being denser falls to the bottom of the oil. Along with this a black coating is observed (Li3N? But I thought that only occurred at higher temps.) This black also sinks. On adding water the black turns white under the oil. The white stuff is fairly soluble in water and can be shown to be the hydroxide. My sample degraded completely over about 3 years in spite of a tight container.
Edited to correct to Li3N
Der Alte


[Edited on 19-6-2012 by DerAlte]

elementcollector1 - 18-6-2012 at 21:18

My samples of lithium (same source, Energizer batteries) have this black coat, but otherwise they're not degrading. If there was a cheap solvent to make them shiny again...
I believe the tarnish is a mixture of hydroxide, carbonate and nitride (I'm pretty sure this forms at roomtemp).
Possible solvents could be anything lighter than lithium (tetralin comes to mind).

MR AZIDE - 19-6-2012 at 10:39


I suppose you could be carefull, and stuff the lithium into petroleum jelly or vaseline, ensuring the lithium is completely incased in it, with no air gap at the top of the storage bottle.

White spirit, contains apparently 100% naphta, which is pretty close to kerosene anyway.

If the lithium floats on this, then why not force the lithium to stay at the bottom of the liquid, by inverting a a smaller container, over it in the main storage bottle, or keeping the lithium in the bottom of the bottle by placing glass wool, all immersed in the storing liquid, above the lithium.

Rogeryermaw - 19-6-2012 at 11:53

many oils and solvents contain dissolved oxygen as they were not produced with the idea of storing reactive metals. http://kamland.lbl.gov/twiki/pub/Main/MuonSpallationTargetMa... this site has data on the solubility of oxygen in a plethora of different fluids. whether or not it works i can't say, but i have been told that it is partially effective to apply vacuum to fluids you wish to store reactive metals in. this will remove some dissolved gasses(so i have been told).

MyNameIsUnnecessarilyLong - 19-6-2012 at 18:08

Quote: Originally posted by DerAlte  
I have often wondered how suppliers of Li metal pack and ship the stuff. Li is so light that any hydrocarbon (SG ~0.89) causes it (SG ~ 0.59) to float largely out of the liquid. Perhaps some of our professional chemists that use the stuff can tell us.



sheet lithium is shipped as a roll inside a round metal can that's been filled with argon and then sealed. Lithium can supposedly be stored like this for decades if the can doesn't get damaged.

lithium blocks are probably shipped this way too

Zan Divine - 19-6-2012 at 18:38

Other sources supply dry ingots vacuum packed in heavy aluminized Mylar.

As far as dissolved oxygen is concerned, if you have the resources you can remove oxygen from most solvents (down to a few ppm level) by vigorously bubbling dry nitrogen or argon through it for 20 - 30 min. This process (purging or sparging) will be somewhat slower in viscous liquids.

Simply applying a vacuum to liquids will bring a large fraction of dissolved oxygen out of solution quickly, but it is nowhere near as efficient as purging.

To minimize resource consumption a home experimenter should use vacuum first followed by a 10 - 15 min vigorous purge.





[Edited on 20-6-2012 by Zan Divine]

Sedit - 19-6-2012 at 18:42

Wrap the Lithium foil around a small glass stir rod or something similar so that the Lithium will sink as this will save you a lot of waste and allow for much longer storage.

Zan Divine - 19-6-2012 at 19:28

Quote: Originally posted by elementcollector1  
Possible solvents could be anything lighter than lithium (tetralin comes to mind).


Neither tetralin nor any other solvent found @ STP in any lab is lighter than lithium. Look all you want, you won't find one.

Even 2-methyl butane has a density of .6201 g/mL at 20 C. Pentane is slightly denser. Butane is a gas. So...

[Edited on 20-6-2012 by Zan Divine]

elementcollector1 - 19-6-2012 at 19:41

Awww.... there goes my college dreams... thanks, Zan. >:P
Anyway, what of a stainless steel mesh net that is submerged in the oil for lithium? Would allow oil flow while keeping the lithium all the way under the oil.

Wizzard - 20-6-2012 at 11:01

Quite possibly a lead...

Liquid butane (.573g/cc) can be stored in a soda bottle at RT, with an internal pressure less than 150PSI. Soda bottles are rated for greater than 200PSI, and I've stored 10 s of cc s on liquid butane at RT for years, one is a demonstration bottle filled only with butane and a bobber, it's very fun to swish around such a light liquid. Or one can keep it in the freezer- Butane is a liquid at -0.5*C. Even a standard soda cap can withstand great internal pressures without leaking or rupturing... The cap I have on even my oldest bottle is only minorly deformed (you would be too, with an internal pressure near the same!). But the amount is nearly unchanged since it was filled.

But back to my point- Dropping an ingot of lithium in a bottle filled with butane will submerge most of the ingot in liquid butane- What's exposed has little chance of oxygen exposure, due to the bottle being backfilled with gaseous butane and with internal pressure. And from from a accidental opening at RT (or violent rupture, should something happen, other than fire!!), it will hiss like an angry bottle of soda, boil off the butane untill it's either back to 0*C or out of butane to boil.

Zan Divine - 21-6-2012 at 06:01

Quote: Originally posted by elementcollector1  
Awww.... there goes my college dreams... thanks, Zan. >:P
Anyway, what of a stainless steel mesh net that is submerged in the oil for lithium? Would allow oil flow while keeping the lithium all the way under the oil.


That would work. But so would filling the bottle all the way up with your mineral oil or whatever you want to use. Sometimes the simplest ideas are the best.

MR AZIDE - 21-6-2012 at 11:45

Of more interest to UK people, but I bought a pack of the Ultimate Li AA size batteries today, from Morrisons market......£3.99.........quite a bit cheaper than most places. Argos are charging £7.49 for the SAME PRODUCT!!

I think £3.99 for a nice lump of Li metal with no questions asked OTC Is a decent price.

Moral, look around for certain things, some places sell really cheap.
BTW I didn't find mineral oil, although there is Baby oil, which is a thinner liquid.

Hexavalent - 21-6-2012 at 11:49

What Morrison's market?

MR AZIDE - 21-6-2012 at 12:01

Morrisons........the Supermarket.......

Hexavalent - 21-6-2012 at 12:07

Oh I see, were they on offer and is it available in all stores nationwide do you think?

MR AZIDE - 21-6-2012 at 12:22

It sounds like you are tempted Hexa...are you not....?????:P

Dont think it was on offer, Morrisons usually to a lot of good offers though. I think it their price thats all. You cant even get these batteries in Homebase.
I wouldve grudger paying £7.49 for batteries Im going to bust open.


kristofvagyok - 21-6-2012 at 12:39

Just a short note for storing lithium.

In the lab we have several kilos of lithium (yes, a lot) what is stored in mainly 2 ways:

1: under argon in a sealed ampoule. This way is used at the small granulated extra pure lithium.

2: under wax in a relative big jar, sealed with some parafilm. Large 50-100g chunks are stored this way and as it looks like, it is there for about 50-80 year now and there is almost no oxide layer on its surface, it is absolutely clean.

And also there is the original package of the chem. suppliers, it floats in parraffin oil, but I think this is the most oxidized from all.
Here is one bottle from Merck:
http://labphoto.tumblr.com/post/22919446779/a-bottle-of-lithium-from-merck-the-black-in-the

Maya - 1-7-2012 at 05:57

would it be preferable to to store long term 2X , 7 pound each , round ingots of Na , 4.5" Dia x 7.5" length,
in either Mylar vacuum sealed bags, or
in Paraffin Oil in a Kautex Jar?
http://www.freundcontainer.com/kautex-wide-mouth-leak-proof-...

The ingots came a long time ago and I still have them in the original packaging, which is basically allota
plastic wrap. Yes, they have developed some oxide coating but that is easily scraped off since they are soo big.
Also what is the best way to cut these beasts up? I am in a non-humidity challenged environment, so AC is on alot.
Thanks for responding

Hexavalent - 19-7-2012 at 10:17

I use white spirits to store my Li and Na - it's clean, very cheap and my source is completely dry, ideal for the storage of these metals.

Panache - 20-7-2012 at 02:46

Seal the elements in carbonite, it stopped Han Solo's human body from decaying so i'm sure it would be fine for Na and Li.

Hexavalent - 20-7-2012 at 07:03

Indeed, where would one obtain some carbonite, Panache?:)

[Edited on 20-7-2012 by Hexavalent]

Random - 20-7-2012 at 07:13

Quote: Originally posted by DerAlte  
I have often wondered how suppliers of Li metal pack and ship the stuff. Li is so light that any hydrocarbon (SG ~0.89) causes it (SG ~ 0.59) to float largely out of the liquid. Perhaps some of our professional chemists that use the stuff can tell us.

My personal experience with a strip extracted from a battery several years ago is that it begins to oxidize immediately, probably to hydroxide due to humidity. This being denser falls to the bottom of the oil. Along with this a black coating is observed (Li3N? But I thought that only occurred at higher temps.) This black also sinks. On adding water the black turns white under the oil. The white stuff is fairly soluble in water and can be shown to be the hydroxide. My sample degraded completely over about 3 years in spite of a tight container.
Edited to correct to Li3N
Der Alte


[Edited on 19-6-2012 by DerAlte]



I was thinking to prevent this, a special bottle could be made.

For example, take pickle jar. In the middle of the pickle jar, you could stick something like a mesh that is not reactive to lithium or mineral oil. Mesh sticked to the middle wouldn't allow the lithium to go upwards.


Random - 20-7-2012 at 07:13

Quote: Originally posted by DerAlte  
I have often wondered how suppliers of Li metal pack and ship the stuff. Li is so light that any hydrocarbon (SG ~0.89) causes it (SG ~ 0.59) to float largely out of the liquid. Perhaps some of our professional chemists that use the stuff can tell us.

My personal experience with a strip extracted from a battery several years ago is that it begins to oxidize immediately, probably to hydroxide due to humidity. This being denser falls to the bottom of the oil. Along with this a black coating is observed (Li3N? But I thought that only occurred at higher temps.) This black also sinks. On adding water the black turns white under the oil. The white stuff is fairly soluble in water and can be shown to be the hydroxide. My sample degraded completely over about 3 years in spite of a tight container.
Edited to correct to Li3N
Der Alte


[Edited on 19-6-2012 by DerAlte]



I was thinking to prevent this, a special bottle could be made.

For example, take pickle jar. In the middle of the pickle jar, you could stick something like a mesh that is not reactive to lithium or mineral oil. Mesh sticked to the middle wouldn't allow the lithium to go upwards.


Dave Angel - 20-7-2012 at 08:28

Quote: Originally posted by MR AZIDE  
Of more interest to UK people, but I bought a pack of the Ultimate Li AA size batteries today, from Morrisons market......£3.99.........quite a bit cheaper than most places. Argos are charging £7.49 for the SAME PRODUCT!!


Wish I'd seen this earlier. I've checked my local Morrisons and all I can find is 2 x AAA for £3.89. Was yours a 2 or 4 pack?

Regarding the storage of lithium, perhaps a good lump of glass fibre wool shoved into the top of a full bottle would keep the metal under, effectively holding it mid-way up in the oil.

Sodium ingots

weldit - 20-7-2012 at 12:57

I bought two large ingots 5 years ago and vacuum packed them. I cut off a piece and store that under toluene. The vacuum packed pieces are still nice and shiny after 5 years

Dave Angel - 21-7-2012 at 04:10

Quote: Originally posted by MR AZIDE  

Moral, look around for certain things, some places sell really cheap.


So true - after my unsuccessful trip to Morrisons I couldn't just give up there.

Check out PC World and Currys - they have 4 x AA Energizer Ultimate Lithiums at £2.97 a pack! Duracells are being pushed so, by the looks of it, they're either doing clearance sales or trying to undercut Duracell.

Needless to say, I'm stocked up now :)

Zan Divine - 21-7-2012 at 06:32

"Perhaps some of our professional chemists that use the stuff can tell us." - Random

This question gets overthought a lot. Just fill the bottle (almost)entirely with whatever liquid you choose.

Most chemists would simply purge empty head space with argon knowing full well that if they need really clean Li a glovebox is the real answer. Most preparative reactions employing Li commonly can tolerate a little nitride/hydroxide so.....

Pyro - 21-7-2012 at 09:19

you know what works wonders for that? vacuum packing.
get your Kg lump of alkali metal, and cut it into 50-150g pieces, depending on how much you use. i use 50g pieces. then take your jar of 50g pieces under oil to a restaurant you know well, and tell them you will give them 5$ to vacuum seal 20 small bags, then put a piece in each bag, with a tiny bit of oil. then vacuum seal it.
that way you can have 50g out at a time, and when you need more you just open the vacuum sealed bag and take out a fresh untarnished one.

Fusionfire - 23-7-2012 at 01:28

Quote: Originally posted by Zan Divine  
Quote: Originally posted by elementcollector1  
Possible solvents could be anything lighter than lithium (tetralin comes to mind).


Neither tetralin nor any other solvent found @ STP in any lab is lighter than lithium. Look all you want, you won't find one.

Even 2-methyl butane has a density of .6201 g/mL at 20 C. Pentane is slightly denser. Butane is a gas. So...



You can store lithium in butane gas. The objective is to displace any potential oxidisers that can react with lithium. Just put it in a glass jar and flush out the air with butane.

Zan Divine - 23-7-2012 at 05:31

Quote: Originally posted by Fusionfire  
Quote: Originally posted by Zan Divine  
Quote: Originally posted by elementcollector1  
Possible solvents could be anything lighter than lithium (tetralin comes to mind).


Neither tetralin nor any other solvent found @ STP in any lab is lighter than lithium. Look all you want, you won't find one.

Even 2-methyl butane has a density of .6201 g/mL at 20 C. Pentane is slightly denser. Butane is a gas. So...



You can store lithium in butane gas. The objective is to displace any potential oxidisers that can react with lithium. Just put it in a glass jar and flush out the air with butane.


Actually, with lithium the objective isn't merely to get rid of oxidizers. Unique among the group 1 elements, lithium reacts with nitrogen even more readily than with oxygen. That's why freshly cut Li turns black (the nitride) rather than white (hydroxide). And both of these degradative pathways require H2O vapor to catalyze them. Gaseous blankets are harder to do well than liquids as you can't see the stuff you missed as readily. Also, most people have better and easier means to dry liquids than gasses.

[Edited on 23-7-2012 by Zan Divine]

edgecase - 23-7-2012 at 05:35

For a source of lithium, has anyone considered the laptop/cellphone battery waste stream?

The PEX tubing used for hot-water (heating) systems comes with an aluminum layer marketed as "oxygen barrier". I believe that is why the mylar packaging also has an aluminum lining like a potato chip bag. Are those available for vacuum sealers?

Obviously glass is good for preventing oxygen diffusion, but the plastic cap of most bottles would allow oxygen diffusion, as would most liquids, so perhaps the aluminum lined lids of scintillation vials (or a piece of aluminum foil), or even a glass stoppered bottle would be best?

Someone has mentioned the baby oil, but maybe that was overlooked so repeating it here.

Although not one of the metals that responds *quickly* to a reducing environment of hydrogen (like mercury would), I wonder if a liquid sparged (ie saturated) or a bottle pressurized with dry hydrogen gas (instead of helium or argon as would normally be done) would maintain or even slowly clean an alkalai metal sample?

Zan Divine - 23-7-2012 at 05:46

Quote: Originally posted by edgecase  
For a source of lithium, has anyone considered the laptop/cellphone battery waste stream?

The PEX tubing used for hot-water (heating) systems comes with an aluminum layer marketed as "oxygen barrier". I believe that is why the mylar packaging also has an aluminum lining like a potato chip bag. Are those available for vacuum sealers?

Obviously glass is good for preventing oxygen diffusion, but the plastic cap of most bottles would allow oxygen diffusion, as would most liquids, so perhaps the aluminum lined lids of scintillation vials (or a piece of aluminum foil), or even a glass stoppered bottle would be best?

Someone has mentioned the baby oil, but maybe that was overlooked so repeating it here.

Although not one of the metals that responds *quickly* to a reducing environment of hydrogen (like mercury would), I wonder if a liquid sparged (ie saturated) or a bottle pressurized with dry hydrogen gas (instead of helium or argon as would normally be done) would maintain or even slowly clean an alkalai metal sample?


No such luck. Hydrogen won't reduce the nitride to Li. The best method is packaging in a sealed ampoule in vacuo or under argon.
http://www.sciencemadness.org/talk/viewthread.php?tid=20125

And, if your seal is subject to diffusion leaks (every temporary seal is), it's all a question of which method fails most slowly.

SM2 - 23-7-2012 at 05:53

Quote: Originally posted by Endimion17  
Kerosene is a worldwide staple for storing sodium.

WD-40 would be OK, but I've just read that the propellant gas isn't butane anymore, but carbon dioxide, which would make a crust on alkali metal surfaces.

I'd suggest you to open your lithium batteries shortly before using lithium. They contain lithium in the form of a foil which is prone to oxidation and crumbling to waste. The only wy to somewhat prevent this is to pack the foil in a small, airtight bottle with as much kerosene/oil as possible, to limit the amount of air above it.


Might it be possible to use, per se., duster, and let that heavier gas sink into the jar. Use a technique where the Li/Na is stored under a non-reactive gaseous blanket?

BTW: Some Li/Gas rxns. are SO endothermic, that they are used by our DOD in some torpedoes. I believe Li+ +SF6 is one of them. I have a big bottle of sulfur hexafluoride if anyone needs that. Even though it's greenhouse rating is like 10K > than CO2, it is completely unrestricted. My aim was to use it in a window soundproofing project, but we ultimately found that cheaper freons did almost as good a job (shich makes sense). Sory of topic again.

SM2 - 23-7-2012 at 06:01

Quote: Originally posted by inspector071  
Do pharmacies in the UK not carry mineral oil as a laxative? They come in 350 mL or so bottles over here in the US.


If you really can't find mineral oil, but need something closely related, just buy some petrolatum, and nuke it carefully just a bit, until it is liquid (before using). But make sure it is hotter than the melt temp., as a hotter petroleum jelly will give up more air bubbles. Of course, what a pain in the ass retrieving and cleaning your ingots when ready to use. My suggestion is probably not a good idea, unless you absolutely want something as close to mineral oil as possible, but can't get the real thing. Fortunately you have better options still.

Panache - 25-7-2012 at 03:00

If your problem is floating Li in a denser, albeit water and O2/N2-excluding solvent, the obvious solution is to simply stopper the flask and turn it upside down.


Pyro - 25-7-2012 at 08:49

vacuum pack it, seriously!

MR AZIDE - 28-7-2012 at 11:06

Quote: Originally posted by Dave Angel  
Quote: Originally posted by MR AZIDE  

Moral, look around for certain things, some places sell really cheap.


So true - after my unsuccessful trip to Morrisons I couldn't just give up there.

Check out PC World and Currys - they have 4 x AA Energizer Ultimate Lithiums at £2.97 a pack! Duracells are being pushed so, by the looks of it, they're either doing clearance sales or trying to undercut Duracell.

Needless to say, I'm stocked up now :)


The last of the batteries were bought........they haven't re-stocked any.
The lithium has been stored under naphta/ white spirits, and weighed down well below the surface of the liquid, and it seems to be keeping OK. Its easy to clean off any of the liquid as well.
Its a bit black, but there are still silvery patches to be seen after a few months.
BTW it was a 2 x AA pack.

Ive read that you can get ultimate advanced lithium batteries, which still contain Li, but are cheaper.......I havent seen them yet.