Sciencemadness Discussion Board - Storing lithium ingots under oil? Density issues?

Storing lithium ingots under oil? Density issues?

Leben - 25-8-2014 at 07:15

I'm going to be getting my hands on some lithium ingots. These are very small, roughly 0.35g, and come packaged in a single aluminum foil fag. I'm going to have roughly about 500g of them.

What would be obvious is to store them under oil, but if I dump a bunch of these in a jar and pour enough oil in to come cover their tops, do I risk them all floating up to the top? Is there an oil that is less dense than lithium that I might could use?

I do not have access to Argon/Nitrogen gas, or else I would put them in a jar and saturate it with gas.

Loptr - 25-8-2014 at 08:09

I believe that petroleum jelly is used sometimes.

Leben - 25-8-2014 at 08:18

I fear that could be a major source of contamination when I go to use my lithium.

Zyklon-A - 25-8-2014 at 08:25

Why not stick a lead spike in your lithium. If you don't have one, it could be easily forged, as lead has a low melting point.

[Edited on 25-8-2014 by Zyklon-A]

unionised - 25-8-2014 at 08:34

Quote: Originally posted by Zyklon-A

Why not stick a lead spike in your lithium. If you don't have one, it could be easily forged, as lead has a low melting point.

[Edited on 25-8-2014 by Zyklon-A]

"These are very small, roughly 0.35g, and come packaged in a single aluminum foil fag. I'm going to have roughly about 500g of them"
About 1400 lead spikes....?

You can always wash the petroleum jelly off when you need to.

Zyklon-A - 25-8-2014 at 08:44

Ok, cast the lithium into a solid mass under a inert gas, in liquid candles/any high temperature boiling hydrocarbon.
Cut into a few chunks.
Stick a ball of lead with a spike into a each lithium chunk.

Mailinmypocket - 25-8-2014 at 09:04

I use a piece of metal window screen pushed into the bottle to hold lithium pieces under their oil. You only need a small square and once it's in the bottle holding the lithium submerged it can be screwed shut no problem.

Loptr - 25-8-2014 at 09:20

Quote: Originally posted by Leben

I fear that could be a major source of contamination when I go to use my lithium.

You would use a solvent, such as diethyl ether, to wash away the petroleum jelly from the lithium.

What I recall from lab is that alkali metals are washed with hexane to remove the oil coating, and then washed with diethyl ether to remove the hexane. IIRC.

[Edited on 25-8-2014 by Loptr]

Fantasma4500 - 25-8-2014 at 09:32

supposing it could be done in a test tube, using simple butane as 'inert gas'
it is heavy and i recall seeing it used for preparing phosphorus sulfide and some other similar compound

MrHomeScientist - 25-8-2014 at 10:13

It's very difficult to find something that lithium won't float on or react with. The metal screen was an idea I had too, and seems the easiest. Woelen stores his under pressurized butane gas, as described in his thread here: http://www.sciencemadness.org/talk/viewthread.php?tid=32593

Keep in mind that unless you completely seal the container (the bag it came in, flame sealed ampoule, etc.) atmospheric gases will eventually find their way in and tarnish your metal.

Leben - 25-8-2014 at 10:23

Quote: Originally posted by MrHomeScientist

It's very difficult to find something that lithium won't float on or react with. The metal screen was an idea I had too, and seems the easiest. Woelen stores his under pressurized butane gas, as described in his thread here: http://www.sciencemadness.org/talk/viewthread.php?tid=32593

Keep in mind that unless you completely seal the container (the bag it came in, flame sealed ampoule, etc.) atmospheric gases will eventually find their way in and tarnish your metal.

I looked into Argon gas and found that I could get 20 cubic feet for around $70, which isn't a bad deal. I think refills are around $20.

Is there a reason why I can't just put the lithium ingots in glass canning jars (with an outer plastic insulator to prevent breakage), and put argon gas in there? Argon is dense enough that no outside gas should be able to find its way in. At this point I am thinking investing in Argon gas is my best option. It would certainly come in handy when doing various reactions.

[Edited on 25-8-2014 by Leben]

careysub - 25-8-2014 at 11:08

Quote: Originally posted by Loptr

Quote: Originally posted by Leben

I fear that could be a major source of contamination when I go to use my lithium.

If you wash the oil off with chilled butane, then it will evaporate immediately once it warms to about 0C, and no further washing would be needed.

MrHomeScientist - 25-8-2014 at 12:36

Quote: Originally posted by Leben

Is there a reason why I can't just put the lithium ingots in glass canning jars (with an outer plastic insulator to prevent breakage), and put argon gas in there? Argon is dense enough that no outside gas should be able to find its way in. At this point I am thinking investing in Argon gas is my best option. It would certainly come in handy when doing various reactions.
[Edited on 25-8-2014 by Leben]

Argon would be a good choice, but again if it's not in a completely sealed container (i.e. ampoule) outside air will eventually leak in. The time scale of that happening may be quite long, but it's virtually unavoidable to my knowledge. Despite being heavier than air, argon is (like all gases) miscible with air. So eventually it will find its way out of the container and come to equillibrium with the surrounding atmosphere.

Not too long ago, I filled a fish tank with sulfur hexafluoride to try to float a tinfoil boat on it. When not playing in it, I laid a lexan sheet over top of it. Despite the very high density of SF6, I was amazed at how quickly it escaped the tank. Within 20 minutes or so. Obviously not well sealed, but it illustrates that these things can escape quicker than you'd think.

Where do you get your Argon? I'd love to have a cylinder handy, especially for my incoming package of lithium metal.

Leben - 25-8-2014 at 12:51

Quote: Originally posted by MrHomeScientist

Quote: Originally posted by Leben

I just searched on google. A ton of sites came up. 20 cubic feet is a ton of Argon too for chemistry purposes.

Air will leak in, that is true, though the seals on those glass jars can be quite nice. And should be fairly sturdy. I will just have to be sure that I purge the jar every use.

careysub - 25-8-2014 at 12:54

Quote: Originally posted by Leben

Quote: Originally posted by MrHomeScientist

Quote: Originally posted by Leben

You could hedge your bets by also putting some of those iron-based oxygen getters also:
http://www.ebay.com/itm/5-2000cc-OXYGEN-ABSORBERS-includes-L...

Any air leakage would be ameliorated by on-going oxygen scavenging.

Leben - 26-8-2014 at 22:59

I just read that Lithium can react with glass and combine with it, but the example was with powdered glass. Will this reaction happen to any substantial extent if I have the lithium floating in oil inside of a stirred flask, like when the lithium contacts the outer portions of the flask?

MrHomeScientist - 27-8-2014 at 05:24

No. The only time I've heard of Li interacting with glass is when the metal is molten. Then it becomes quite scary.

Dr.Bob - 27-8-2014 at 07:27

As long as the lithium is in mineral oil, and in a sealed glass jar, it should be OK. No matter how careful you are, it will slowly oxidize, but there is enough mass there that the top pieces will act as oxygen getters.

I would rinse the lithium with hexanes in a flask to remove any oil. It is not that tough, and just keep those hexanes in another sealed jar, as they may get specs of lithium in them, so be careful not to leave uncovered. Once you get enough used hexanes, just let them sit in a safe place, open a short time, to quench any lithium and then you can distill them to recover most of the hexanes.

Traces of oil are harmless to most chemistry and will not affect most reactions.

eBay Chinese Lithium

careysub - 30-8-2014 at 11:02

I bought one of those packets of 25 g of lithium ($20) from yaolihong2013 on eBay, which arrived in a double pouch.

The outer pouch is opaque aluminized plastic so you can't see what is inside, which was a clear plastic pouch with bright shiny pieces of lithium wire (large surface area).

The clear pouch is a notched rip-open type, which I judged rather fragile, so I stuck it in a 16 oz mason jar for mechanical protection.

I figured that as long as the inner pouch was intact, that the lithium would be safe from oxidizing.

Wrong. 10 days later it has mostly blackened. Be forewarned if you get some of this.

Either do not open the outer packet (until you are ready consume it in some manner), or have a plan to store it in another container ready-to-go.

I am planning on ordering another packet, I suppose I will follow the observation that lithium pieces in jar act as their own getter, the top layer tarnishing but protecting the bottom, and put the now-blackened lithium on top of new shiny lithium.

Those iron oxygen scavengers should work also I think. One company actually fills its packets with a mixture of finely divided iron and mineral oil. Immersing packets in the oil should not interfere with their function.

I think these should do the trick (50 cc packets capable of de-oxygenating 400 ml container; 10 of them for $3 shipped):
http://www.ebay.com/itm/50cc-Oxygen-Absorbers-10-sachets-pac...

[Edited on 30-8-2014 by careysub]

careysub - 31-8-2014 at 05:43

Quote: Originally posted by Dr.Bob

As long as the lithium is in mineral oil, and in a sealed glass jar, it should be OK. No matter how careful you are, it will slowly oxidize, but there is enough mass there that the top pieces will act as oxygen getters.
...

Since lithium floats, if you purge the jar with inert gas, and then invert it for storage, I wonder whether this will prevent oxygen infiltration.

Also I suggest wrapping the jar threads with PTFE ("teflon") plumbers tape.

A poster on the sodium storage thread boils his mineral oil first, which seems likely to be helpful to drive out dissolved gas and water. To really boil it you must heat it to around 350C.

It appears that mineral oil can dissolve about 50 ppm at 20C, and that the solubility increases with temperature (200 ppm at 50C), so getting substantially hotter than water's boiling point in going to be necessary to drive it off:

http://www.nttworldwide.com/tech2204.htm

[Edited on 31-8-2014 by careysub]

FireLion3 - 31-8-2014 at 19:49

Quote: Originally posted by careysub

I bought one of those packets of 25 g of lithium ($20) from yaolihong2013 on eBay, which arrived in a double pouch.

The outer pouch is opaque aluminized plastic so you can't see what is inside, which was a clear plastic pouch with bright shiny pieces of lithium wire (large surface area).

The clear pouch is a notched rip-open type, which I judged rather fragile, so I stuck it in a 16 oz mason jar for mechanical protection.

I figured that as long as the inner pouch was intact, that the lithium would be safe from oxidizing.

Wrong. 10 days later it has mostly blackened. Be forewarned if you get some of this.

Either do not open the outer packet (until you are ready consume it in some manner), or have a plan to store it in another container ready-to-go.

I am planning on ordering another packet, I suppose I will follow the observation that lithium pieces in jar act as their own getter, the top layer tarnishing but protecting the bottom, and put the now-blackened lithium on top of new shiny lithium.

Those iron oxygen scavengers should work also I think. One company actually fills its packets with a mixture of finely divided iron and mineral oil. Immersing packets in the oil should not interfere with their function.

I think these should do the trick (50 cc packets capable of de-oxygenating 400 ml container; 10 of them for $3 shipped):
http://www.ebay.com/itm/50cc-Oxygen-Absorbers-10-sachets-pac...

[Edited on 30-8-2014 by careysub]

Lithium doesn't react with Oxygen it reacts with Nitrogen (and water). The black layer that forms on the outside is Lithium Nitride (a strong base), so oxygen scavengers are unlikely to work. You will need to store it under inert gas or in oil.

Quote: Originally posted by careysub

Since lithium floats, if you purge the jar with inert gas, and then invert it for storage, I wonder whether this will prevent oxygen infiltration.

Assuming you can get a container that is fairly air tight, storing under a heavy inert gas should do the trick just fine for relatively long periods of storage.

careysub - 1-9-2014 at 07:44

Quote: Originally posted by FireLion3

...

Lithium doesn't react with Oxygen it reacts with Nitrogen (and water). The black layer that forms on the outside is Lithium Nitride (a strong base), so oxygen scavengers are unlikely to work. You will need to store it under inert gas or in oil.

Quote: Originally posted by careysub

Since lithium floats, if you purge the jar with inert gas, and then invert it for storage, I wonder whether this will prevent oxygen infiltration.

Assuming you can get a container that is fairly air tight, storing under a heavy inert gas should do the trick just fine for relatively long periods of storage.

You are saying that it does not also react with oxygen at ambient temperature? The higher reactivity of oxygen, and the existence of the lithium-air battery that relies on room temperature oxidation (with oxygen), makes that seem unlikely to me.

But if it reacts with nitrogen then oxygen scavenging is obviously not going to solve the problem.

Lithium reacts with carbon dioxide also, so "inert gas" here would be helium or argon, I guess. Helium's small, light atom makes it hard to contain (but it might work in my suggested inverted jar storage configuration), so that leaves argon as the go-to gas.

Bloxygen, an aerosol can (containing no aerosol, just the gas) with 12 g of argon (6.7 L) is available for $12.50 shipped from Hartville Tool for those who do not want to invest in a $90 gas cylinder. I just ordered one.

I was surprised that the argon-flushed sealed inner plastic packet did not resist infiltration for even a few days. I am not confident whether any of my jars/bottles are intrinsically much tighter, so I want to get all the protection I can.

I will use the teflon tape trick as an assist, and I'll ship around for a really tight bottle. A Qorpak perhaps?

Mason jars, when heat sealed, do hold vacuums well (years, even decades). Perhaps I should try heating the top with a heat gun to seal it since I don't want to autoclave the entire jar.

[Edited on 1-9-2014 by careysub]

[Edited on 1-9-2014 by careysub]

[Edited on 1-9-2014 by careysub]

FireLion3 - 4-9-2014 at 17:20

careysub,

It was probably wrong for me to say it doesn't react with air. Lithium is very reactive and probably reacts with a lot of gases. Lithium is known for forming a black Lithium Nitride layer on its surface when left in the air. I suppose this would be your main worry seeing as air is composed of mostly nitrogen.

I am not sure you would need to heat seal the mason jar. If you use Argon and seal the lid decently, assuming it is not tossed around, a large majority of the air will be kept out. Even if the seal is not complete, argon being heavier than air will keep most of the air at bay.

I am designing a container that utilizes gas-check valves. Something that I can seal, then put argon in through the 1 way in port, while the lighter air gets pushed out of the 1 way out port. This will be an effective way to purge almost all of the lighter air out of the container. After purging is complete, just close off the intake port, and you would have a mostly perfectly inert sealed container. - Cruicial is the lid, but I'm sure you can figure that most. Many premade containers can be modified fairly easily to work in this manner.

The Volatile Chemist - 4-9-2014 at 17:31

I suppose balloon helium has reactive gasses in it, I guess.

Quote:

aluminum foil fag

like to meet one of those.

Couldn't you just fill a jar w/ a nonreactive oil, plop the lithium in, close the jar, then flip it upside-down? I guess that defeats the ease of using it, though.
Sounds like you got a pretty big lot of lithium! Where'd you get it?

subsecret - 4-9-2014 at 18:09

You could put a beaker on top of the lithium, pushing it into the oil. If the bottom of the beaker is too narrow to fit the jar, use an appropriately-sized watch glass.

Dr.Bob - 4-9-2014 at 18:20

Plastic id much more air permeable than glass, that is why soda goes flat in plastic quicker than glass, and each type of plastic is different in what goes through it faster. But if you put the plastic bag in a glass jar and seal it, it will help a lot, especially if you can purge it with argon first. Helium diffuses much faster than argon, so argon is better.

No metal will last forever if not sealed well, but a layer of surface tarnish will not be a big issue for most chemistty, I have used lousy looking sodium and it works just fine. The only time the appearance will matter is for use in pretty element displays, and that will require a sealed ampule or glass jar full of oil to really keep the metal clean.

careysub - 5-9-2014 at 05:37

Quote: Originally posted by The Volatile Chemist

I suppose balloon helium has reactive gasses in it, I guess.

The Balloon Time MSDS claims that their product is 100% helium:
http://www.balloontime.com/about/warnings-precautions.aspx

Frankly I am dubious.

I expect they are filling welding helium which has a minimum purity of 99.995% into a tank that already contains air. The tank has a pressure of 260 PSI, so this would result in 95% helium, 4% nitrogen and 1% oxygen.

The Bloxygen people are selling their product specifically as an inert gas, so I believe they have a pure argon product.

Quote: Originally posted by The Volatile Chemist

Couldn't you just fill a jar w/ a nonreactive oil, plop the lithium in, close the jar, then flip it upside-down? I guess that defeats the ease of using it, though.
Sounds like you got a pretty big lot of lithium! Where'd you get it?

Yes, the inverted oil jar is something I am considering (I mentioned it above), but if it has a gas space it still needs to be flushed.

What is a "big lot" of lithium? I have 50 g right now, bought at a good price of eBay. There is a Chinese vendor offering 25 g for $20, of $0.80 per gram. GalliumSource charges $1.10 per gram on amounts of 100 g.

When you consider the price per mole, that is $5.50/mole. Someone on this site is offering sodium at $100/lb which works out to almost the same: $5/mole. If you need an alkali metal for a reduction the lithium is attractive.

The lithium though is special case of a more general problem (storing air-reactive materials) and there are more than a few of those in a complete element collection, so the merits of various options is of interest to me.

I think I am going with putting the inner bags of lithium in an argon-flushed mason jar, with PTFE tape on the threads, and heated to activate the rubber seal (I'll experiment with some empty jars first.)

Hmm.. I do have a partially used old BalloonTime tank. Perhaps I should pre-flush a storage jar with the no-doubt air contaminated helium to get some use out of it, then flush with Bloxygen argon.

For an element display lithium in an inverted mineral oil filled culture tube (with screw cap) would be good. Seal the cap (after tightening) with silicone perhaps?

[Edited on 5-9-2014 by careysub]

[Edited on 5-9-2014 by careysub]

The Volatile Chemist - 5-9-2014 at 12:45

I was talking about Leben's 500g. But I didn't know it was that cheap.

Quote:

Yes, the inverted oil jar is something I am considering (I mentioned it above), but if it has a gas space it still needs to be flushed.

Just do it in a basin of oil, with the jar submerged. I suppose silicone and many other thins would work.

MrHomeScientist - 10-9-2014 at 10:59

careysub, I also bought lithium from that supplier and received it a couple days ago. How was the quality of yours, when you first removed it from the package? Mine was already pretty tarnished. Still decent looking, but nowhere near the quality of the listing's picture. I also got two bags - one was packaged as you described, and the other has both outer and inner packages as the metal foil. I'm hoping the inner foil packet holds up better than the clear plastic one. I wanted at least one of these for a high quality element display :/

careysub - 10-9-2014 at 11:25

Quote: Originally posted by MrHomeScientist

careysub, I also bought lithium from that supplier and received it a couple days ago. How was the quality of yours, when you first removed it from the package? Mine was already pretty tarnished. Still decent looking, but nowhere near the quality of the listing's picture. I also got two bags - one was packaged as you described, and the other has both outer and inner packages as the metal foil. I'm hoping the inner foil packet holds up better than the clear plastic one. I wanted at least one of these for a high quality element display :/

I ordered two, both came with the foil outside packet, with the clear tear-open style packet (discovering this requires sacrificing the outer packet obviously).

Both were bright and shiny as received.

I currently have them both in a quart mason jar that I flushed with Bloxygen argon gas. The new bag went in day before yesterday.

One problem with the Bloxygen, is I am uncertain if I have flushed enough. The jar is 1 qt, the can holds 6.7 L of argon. I guess I should just empty the rest of the can into it, and time how long that takes, then I would roughly know the rate of emission (I will have to estimate my time for the first flush) for future possible use.

I just found Bloxygen cans are available for $8.50 at Austin Hardwoods in Santa Ana, CA.

If I feel the need to buy more than a couple of cans I should invest in a 15 lb gas cylinder and get argon from Praxair. They may be in my future if I work with reactive substances much.

MrHomeScientist - 16-9-2014 at 19:30

So I also bought some of the Chinese lithium (2 orders of 25g each), and it was packaged as one envelope with two metallic packets inside. In the first metallic pouch was a second clear plastic pouch that contained the Li metal. The other metallic pouch contained a second metallic pouch that feels like it contains the metal (this one isn't transparent). The metal I received was significantly tarnished from the minute I got it, after opening the outer packet but leaving the inner clear plastic one intact. It wasn't terrible, but wasn't nearly as clean as the listing's picture claimed. I tried complaining to the seller but, predictably, he replied with poorly translated gibberish like "Dear friend. Pretty only 96.5% purity lithium lithium is you receive a high purity. I hope you understand."

So I ordered a couple cans of the Bloxygen stuff careysub mentioned to try to save it - really great find by the way, thanks a lot for that tip. It took about a week to arrive, and all the while the lithium in the plastic pouch continued to tarnish despite being completely sealed. When I got my Bloxygen, I fumbled around a bit but managed to get it all in a pyrex media bottle that I had purged with Bloxygen argon. I sealed the cap with yellow gas-tight plumber's teflon tape, and wrapped the outside with parafilm for good measure. Not sure if parafilm does much of anything, but it couldn't hurt. Anyways here's a picture of what I've got now. Still slightly shiny but quite blackened. I'm very surprised how permeable that plastic packaging was, and how quickly the Li has darkened.

That's one of the 25g packets. The other portion is still in its inner metallic pouch, which I hope holds up better than the clear plastic one did. I'm trying to find a more permanent storage solution for that batch, and one which will look nice for display in my collection (assuming that pack is less tarnished).

Dr.Bob - 17-9-2014 at 05:07

Having done a lot of work with reactive chemicals in my days, I can say with great assurance that nearly any container with a closure (lid, cap, screw top, etc) will leak some amount of air and water through it. Also, any polymer will let various amounts of both through, some are better at resisting water or airt than others, but few plastics are very resistant to water and air permeation at the level needed to protect reactive metals.

A glass ampule is really the best solution to keeping chemicals fresh that I have seen, I have handled chemicals in ampules that might have been 10-20 years old that still looked fresh and clean. Comparably, still sealed glass bottles, never opened, have shown large amounts of reaction after periods of days to years, depending on the closure.

But a simple jar full of mineral oil will suffice for most storage of reactive metals being used for chemistry, as the oxide/nitride layer will not be a big issue for most chemistry that I have ever seen. Making sodium methoxide, for instance, most people just cut a clean chunk or several (if the scale is big, you may need to use a lot of smaller pieces), then add it slowly to the methanol (under argon) or put it in a flask with an inert solvent and slowly add the methanol to it. For the chemistry I have done, that provides perfectly good NaOMe, even with bottles of sodium that look 20 years old.

jamit - 25-9-2014 at 01:11

Hi careysub and mr homescientist -- I also ordered from the Chinese supplier and just as pictured by homescientist, it comes already tarnished with the black crud. Has anyone tried melting it?

careysub - 25-9-2014 at 06:50

Quote: Originally posted by jamit

Hi careysub and mr homescientist -- I also ordered from the Chinese supplier and just as pictured by homescientist, it comes already tarnished with the black crud. Has anyone tried melting it?

I guess I got lucky with my two shiny samples.

I am considering melting it into ampoules, or a test tube for storage, but I plan on getting a regular argon gas bottle first so that I can purge to my hearts content - even purge a small handling box for when I crack open my Mason jar.

I figure than if you put all the lithium in a test tube/culture tube and melt it down it will stick to the glass and stay on the bottom. Then pour in a little degassed mineral to fill to the top and seal.

MrHomeScientist - 25-9-2014 at 06:57

Doesn't molten lithium react with glass? Very quickly?

Edit:
Found this document detailing precautions when handling lithium. It doesn't mention the glass reaction (even though the google link to it says it does), but I did see this interesting bit:
"The reactivity of molten lithium is much greater than solid lithium. Blanketing with argon or dry air is recommended to
protect the metal and to minimize the possibility of fires. Molten lithium reacts explosively with concrete flooring, and any area
wherein a liquid lithium spill may occur must have welded steel flooring."

That sort of puts a damper on my planned experiments on the back porch.

[Edited on 9-25-2014 by MrHomeScientist]

Attachment: LithiumHandlingURC.pdf (14kB)
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Edit 2:
Here we go:
Attachment: The Alkali Metals.pdf (3.9MB)
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From that source:

[Edited on 9-25-2014 by MrHomeScientist]

careysub - 25-9-2014 at 11:39

Quote: Originally posted by MrHomeScientist

Doesn't molten lithium react with glass? Very quickly?
[Edited on 9-25-2014 by MrHomeScientist]

I guess I won't be melting my lithium in a test tube then!

I see that molten lithium does not react with "low carbon stainless steels". Also, it doesn't react with tungsten or moylbdenum.

I guess I can cast my lithium into an ingot using a stainless steel mold, in a stainless steel, argon-flooded crucible. The coefficient of thermal expansion of lithium is about 46*10^-6 k, over 4-6 times larger than stainless steels so the lithium should separate from the mold on cooling.

You could cast a piece of stainless steel, Mo or W into the lithium ingot as a permanent anchor, and have the mystery of the sinking lithium to puzzle your friends.

MrHomeScientist - 25-9-2014 at 12:42

I had planned on using my lithium for the final stage in my 'neodymium from magnets' project, by mixing it with NdF3 and heating in a crucible. The only crucible types I have are fused silica (probably no good because of the whole 'glass reactivity' thing) and graphite. I'm wondering about graphite now, since low carbon steels was mentioned. What happens when it's all carbon? The last thing I'd want is to form lithium carbide which could produce acetylene and explode my furnace

I do have stainless steel condiment cups, perhaps that's an option?

Dan Vizine - 16-10-2014 at 10:49

I've had a bit of experience handling molten lithium. At low temperatures (say, <500 C), you can use many common metals for molten lithium. I've used SS in the 300 series, like 302, 304 & 316, as well as mild steel.

No commonly available ceramic or glass is appropriate. Yttria stabilized thoria is the best ceramic, with only minor attack after 1000 h @ 1093 C.
Sample Temp (C) Time (hr) Results
BeO 1093 500 Significant attack, Li penetration
MgO 1093 100 Disintegrated
Y2O3 1093 1000 Slight attack
ThO2 1093 1000 Slight attack
ThO2 -5% Y2O3 1093 1000 Very minor attack
AlN 1093 1000 Severe cracking
BN 1093 100 Disintegrated
TiC 1093 2000 Some cracking
MgAl2O4 1093 100 Disintregated

At elevated temperatures, the situation changes a bit:
Lithium—a vessel fabricated in the 1970’s of RA333 for the US Navy liquid metal
embrittled & cracked from residual stress in the formed head, when operated 1650°F
(900°C) with molten lithium. Had we been asked, we would have suggested first annealing
the head to remove forming stresses. Corrosion of RA333 occurs primarily by selective
leaching of the nickel. Alloy X behaves in a similar manner. Based on laboratory tests,
TZM molybdenum and pure iron (to 1000°C) are said to have good resistance to molten
lithium corrosion. Ferritic stainlesses are said to be subject to chromium leaching.
However E-Brite was found more resistant to molten lithium than either nickel or cobalt
base alloys. These are laboratory test results, not necessarily confirmed in service.

I've attached a small collection of references which deal with lithium. There is a lot of practical information sprinkled throughout.

Attachment: Lithium & Ceramics.PDF (35kB)
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Attachment: Lithium Combustion.pdf (2.9MB)
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Attachment: Lithium Handling.pdf (64kB)
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Attachment: Lithium Properties.pdf (3.2MB)
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And, here's a quote from "The Encyclopedia of Chemical Elements" by Clifford Hampel and published in 1968 by Reinhold.
"Lithium can be melted and poured in dry air without losing its luster and it does not react with dry oxygen below 100 C"

With lithium, its ALL about the moisture. Without catalysis by 5 ppm or more H2O, Li is indifferent to both oxygen and nitrogen.

At high temperatures, lithium reacts with elemental carbon to give the acetylide. Exactly what constitutes "high" wasn't specified in the above encyclopedia, although the definition that is generally accepted now is that anything above 500 C is a high temperature process.

A note about storage...no plastic will keep lithium shiny for long. It's because of what makes plastics plastic, the long chains, loosely organized at best, just can't stop oxygen diffusion. Only metals, glass or metallized plastics will work. And speaking of work, if it's got a screw cap, it won't. Or not for long anyway. The unstoppable force of diffusion never gives up, and so, oil or no oil, lithium in a screw cap bottle eventually darkens. Always. Only a "total" seal, like an ampoule or the heat-welded metallized bag that it comes in, is good enough for long term storage.

There isn't a real danger of molten lithium - concrete explosions unless you have a whole lot of liquid metal. Otherwise it just splashes like solder does, and it cools quite quickly. I've done it more than once.

Another noteworthy factor when melting Li in air, once a nucleus of this cauliflower-looking solid mat (a mixture of the nitride and other species) forms on the surface of the liquid metal, fire is going to happen. This is catalysis out of control. It's not a big deal (not a flash), except that it's very, very difficult to extinguish. Carbon powder is suggested, but I usually just let it burn and turn the exhaust fan on. The amounts that I melt are modest, usually just 5 - 20 g at a time.

[Edited on 16-10-2014 by Dan Vizine]

MrHomeScientist - 21-10-2014 at 13:20

Fantastic info Dan, thanks very much for posting. I'm reading through the attachments now. So you've used stainless steel as your crucible for melting Li, then? What sort of temperatures have you achieved with molten lithium? My experiment is going to produce over 1024 C, so this will probably be a much more unforgiving environment. (This is for my neodymium isolation via 3Li + NdF₃ == Nd + 3LiF)

From your second PDF: "Of the refractory metals, columbium, tantalum, and molybdenum are relatively stable at 1000°C". This is interesting because I happen to have tantalum foil, so it's possible I could line my crucible with Ta to protect against attack. On the other hand, wikipedia mentions, "[Ta] can be dissolved with hydrofluoric acid or acidic solutions containing the fluoride ion" - there will be fluoride in the mix so that may cause problems. Any thoughts on that?

From the same source: "Various materials were subjected to a 1/16-inch-diameter stream of lithium at 590*C and 60 psig for 30 seconds. The materials were positioned 6 feet from the orifice and were sprayed with 3.2 kg of lithium."
That sounds FUN

j_sum1 - 21-10-2014 at 15:22

If you wanted to use Molybdenum, I have located a refractory boat for five dollars. http://www.tungsten.com/orphan.html
It could be good for a lithium melt.

The Volatile Chemist - 23-10-2014 at 06:51

Is it that trust-able?
Never heard of the co. before.

j_sum1 - 24-10-2014 at 01:04

Well they have been round a while and update their "orphan" list every few months. Communication seemed very professional. But I guess it is a small business operating only a few days per week. I have been waiting for email reply for a couple of days and that is unusual. We will see how my current order goes.
There is nothing to suggest they are not legit.

The Volatile Chemist - 31-10-2014 at 05:34

It looks cool. I mean, why not buy some tungsten foil or molybdenum disks! I would, but I have parents...Maybe later.

MrHomeScientist - 31-10-2014 at 05:46

Why not? There's nothing hazardous about tungsten and molybdenum! Unless you drop the tungsten on your foot.

diddi - 31-10-2014 at 16:25

My post on storage got lost, so here it is again. I have tried 2 methods that have been reasonably successful. firstly to sink my Li in oil, I use a jar with straight sides and I cut a clear disk of about 3 mm plastic to fit tightly in the jar. I polished the edge of the disk and drilled a few small holes to allow the oil to pass through. then I use it to force the Li under the oil. it is great for display as the polished disk is virtually invisible and the Li appears to float in the middle of the jar.

Re argon gas procurement. by far the cheapest argon you will ever get is to find a mate with a MIG or TIG welder who uses 100% Ar (not the CO2/Ar mix) and borrow a bit. the amount you use will cost about 10cents. I use welding Ar with Li and so far it has worked well. I am using this for my investigation into REE storage as per other thread on that topic.

@mrhomescientist I bought some Li from that supplier you described. I had a foil packet with a clear packet inside. the foil was under Ar, but I found the problem with the supplier's packaging was to do with the hot melt plastic bag sealer he uses. it has a cold spot. I looked at the seal on the clear bag which had been heat sealed twice, but the small breach in the heat pattern allows air to slowly enter the "seal" and guess what, my pristine Li started to tarnish overnight because I did not see the breach. I purchased another item from this supplier which arrived in very poor condition due to inappropriate packaging. we sorted out the problem to both our satisfaction so creds where deserved.

[Edited on 1-11-2014 by diddi]

The Volatile Chemist - 2-11-2014 at 12:27

Quote: Originally posted by MrHomeScientist

Why not? There's nothing hazardous about tungsten and molybdenum! Unless you drop the tungsten on your foot.

Haha, my parents just don't like me buying things on-line, though they've gotten used to Amazon. They also wouldn't like me spending $35 (the minimum purchase) on one or two things. They also prefer micro-chemistry to standard chemistry.

aga - 2-11-2014 at 15:31

All Safety is an illusion.

Micro, Macro, Inbetweeno ...

Basically there is no 'safe'.

A meteorite could splatter you at Any moment, no matter what you do.

'Staying Safe' just means 'Minimising the probability of accidental death'

As Douglas Adams said: a million-to-one chance happens nine times out of ten.

j_sum1 - 17-11-2014 at 03:14

Quote: Originally posted by j_sum1

If you wanted to use Molybdenum, I have located a refractory boat for five dollars. http://www.tungsten.com/orphan.html
It could be good for a lithium melt.

Quote: Originally posted by The Volatile Chemist

Is it that trust-able?
Never heard of the co. before.

Took a bit of discussion to get the freight price down (USA to AUS), but today I received my shipment of tungsten plate, wires and filaments as well as some molybdenum foil. Looks nice.
If anyone is still looking for W or Mo then I can report a positive experience.

gdflp - 10-5-2016 at 15:51

Just received some lithium(50g) from yaolihong2013 and it looks like I got lucky. I opened both the inner and outer packet at the same time and put it straight under mineral oil, see below. There is some oxidation on the surface, but very little unlike MrHomeScientist's. I've only opened one of the two 25g packets so far, I'm debating whether the second packet will last longer if I leave it in the hermetically sealed original packaging, or put it under oil as well. Anyone have any insight they can offer?

elementcollector1 - 10-5-2016 at 16:00

Quote: Originally posted by gdflp

Just received some lithium(50g) from yaolihong2013 and it looks like I got lucky. I opened both the inner and outer packet at the same time and put it straight under mineral oil, see below. There is some oxidation on the surface, but very little unlike MrHomeScientist's. I've only opened one of the two 25g packets so far, I'm debating whether the second packet will last longer if I leave it in the hermetically sealed original packaging, or put it under oil as well. Anyone have any insight they can offer?

I think you should put it under oil - I'm not sure how transparent the hermetically sealed packaging is, but at least under oil you'd be able to tell how the sample was doing.

gdflp - 10-5-2016 at 16:30

The outer packing is a silvery color and is opaque. The inner packing is clear, but based on the experience of others in this thread, I definitely don't want to leave it in that alone.