Sciencemadness Discussion Board - Thionly chloride from batteries

Thionly chloride from batteries

Monoamine - 25-6-2021 at 10:14

Warning: Thionyl chloride produces toxic SO2 gas and HCl gas. User discretion is advised.

I recently saw that it's quite common to find so called "Li-SOCl₂" batteries for sale. These batteries consist of a solid lithium anode and a liquid cathode made of SOCl₂. Considering that most chemical suppliers in the west won't sell this nasty reagent to individuals, this would seem like a found treasure indeed!

Has anyone here tried this before and what was yoir experience?

njl - 25-6-2021 at 16:27

I've looked into it a little, they seem very expensive for a frankly tiny amount of SOCl2

paulll - 25-6-2021 at 17:13

Quote: Originally posted by njl

I've looked into it a little, they seem very expensive for a frankly tiny amount of SOCl2

That was my initial impression, I'd hoped there was more to it. Even if one could get a big whack of these things for little outlay I can't see getting a useful stock of clean thionyl chloride out of it. Still hoping I'm wrong, though!

draculic acid69 - 26-6-2021 at 00:11

Apparently~48% of the battery weight is thionyl chloride I read somewhere. If true it would be a viable option for small amounts

Oxy - 26-6-2021 at 05:11

I checked SDS of one of the batteries and there is 40-45% SOCl2 by mass, so you're right draculic acid69.
However, the battery costs ~10 Euros and it's mass is 26 grams so it means there is ~10.5 grams of thionyl chloride which is 0.0874 mole.
Kind of expensive source, but maybe if there is a cheaper source of batteries (China?).

BromicAcid - 26-6-2021 at 06:15

Doesn't seem entirely bad for a sealed, shippable, one-time source of thionyl chloride. Long ago I purchased a 6-pack of sulfur dioxide / lithium batteries. They were very useful for quick sulfur dioxide experiments.

draculic acid69 - 26-6-2021 at 07:26

It won't get U a stock supply of the stuff but enough for a small experiment or two. It might not be value for money when compared to buying a liter but for a small amount with no hassles it's a good enough deal

draculic acid69 - 26-6-2021 at 07:30

Quote: Originally posted by Oxy

But maybe if there is a cheaper source of batteries (China?).

Of course China. It's always China.

draculic acid69 - 26-6-2021 at 07:32

Strangely enough no one has asked how much lithium is in them.
How much lithium is in them? Anybody?

[Edited on 26-6-2021 by draculic acid69]

karlos³ - 26-6-2021 at 09:42

I think in the preparation of the horribly dirty drug thats called "krokodil", they use SOCl2 from batteries for the first step, the chlorination of codeine to alpha-chlorocodide(from which the name krokodil apparently stems, from mispronounciation).
We know how they proceed further, no need to mention this.

I just mention it because it, well, somehow, illustrates the usefulness of these batteries for OTC thionyl chloride.
If such people can use it reliably(I doubt they distill it, crack the battery open and collect the liquid, thats it at most!), then its likely a good source for amateurs who actually know how to purify that stuff.
Expensive of course... I would guess that the russian junkies just steal them instead :

Oxy - 26-6-2021 at 10:11

Quote: Originally posted by draculic acid69

It won't get U a stock supply of the stuff but enough for a small experiment or two. It might not be value for money when compared to buying a liter but for a small amount with no hassles it's a good enough deal

I always forgot that there is no need to buy a large supply all the time, of course you're right.

I checked another battery and it's SDS says that depending on the model there is 18-47 percent of thionyl chloride and 2-6% of lithium metal.

So, before buying it is a good idea to check given model and it's SDS

draculic acid69 - 26-6-2021 at 21:44

So for a 26 gram battery there will be a gram or so of lithium.

Mush - 27-6-2021 at 07:34

Similar topic.
http://www.sciencemadness.org/talk/viewthread.php?tid=154324

"The traditional synthesis of desomorphine starts from α-chlorocodide, which is itself obtained by treating thionyl chloride with codeine." WIKI

In Russia, AFIK the clandestine approach is HI/P reduction, in one step.

I have never tried but I would imagine to extract the SOCl2, DIY Glove Box is needed to work in an oxygen free atmosphere. Mainly because of the lithium fire hazard.

Journal of Power Sources, 4 (1979) 1 - 9
THE LITHIUM-THIONYL CHLORIDE BATTERY - A REVIEW

Attachment: The_Lithium-Thionyl_Chloride_Battery_A_Review.pdf (492kB)
This file has been downloaded 421 times

Attachment: LITHIUM THIONYL CHLORIDE BATTERY.pdf (964kB)
This file has been downloaded 394 times

[Edited on 27-6-2021 by Mush]

Monoamine - 30-7-2021 at 17:16

Interesting! And yes, definitely want to be careful with the lithium, although considering that not even sodium metal immediately bursts into flames in air, I'd imagine that if you quickly drain out the SOCl2 and then fill the pattery with paraffin you should probably be ok... (but wearing a blast shield and keeping a fire extinguisher nearby would definitely not be unwise).

Monoamine - 30-7-2021 at 17:19

Also, I came across a chemical vendor in India who sells SOCl2 and seems quite legit. In my experience Indian and Chinese chemical vendors tend to be less uptight than in some other countries. Always had good experiences with them, so it might be worth a shot...

[Edited on 31-7-2021 by Monoamine]

teodor - 31-7-2021 at 04:27

In the old good book "Die chemie in wasserähnlichen losungsmittelen" G. Jander there are examples of decomposition of higher chlorides in liquid SO2 :

PCl5 + SO2 = POCl3 + SOCl2
NbCl5 + SO2 = NbOCl3 + SOCl2
WCl6 + SO2 = WOCl4 + SOCl2

They are actually were used as synthetic routes for corresponding oxychlorides preparation because when you try to use water for the preparation it is unable to stop its solvolytic action and hydrolises goes usually till you get HCl and corresponding oxide. With SO2 as a solvent you can get oxychloride and SOCl2 as a byproduct in those cases when you get oxide & HCl with water.

Why I am talking about that?

Well, I think that investing in good lab equipment which will allow you to work with liquid SO2 is better than investing in expensive thionyl chloride batteries which will allow you to get a minute amount of impure SOCl2 which is almost impossible to safely distil in typical amateur settings. Also this equipment will allow you to explore much more interesting things than even re-distilled SOCl2 .

karlos³ - 31-7-2021 at 12:08

Quote: Originally posted by Mush

Similar topic.
http://www.sciencemadness.org/talk/viewthread.php?tid=154324

"The traditional synthesis of desomorphine starts from α-chlorocodide, which is itself obtained by treating thionyl chloride with codeine." WIKI

In Russia, AFIK the clandestine approach is HI/P reduction, in one step.
...

Both actually, not to drive this topic off, and I don't know how they do that in practice, but I know from the limited forensic stuff thats out that its actually the chlorocodide produced first from the codeine pills(usually without extraction), and then they do a HI/P reduction, which dehalogenates and simulatenously demethylates the still remaining ether.

I actually wonder more about how that would be done, the cracking open of the batteries, and how the further use would be done?
I assume, their technique is neccessarily streamlined, but likely only told by oral history...

I don't if that phenomenom even persists to this day, I believe not.
But their technique for opening the batteries(a junky doesn't care they're overpriced, he steals them) would be pretty interesting for sure.
For those who would attempt this task, at least.

Panache - 7-8-2021 at 02:23

Theres bound to be a youtube vid of someone doing the entire synth in a walmart aisle soon....

Extraction and crude purification notes and procedure

Monoamine - 7-8-2021 at 18:21

Ok, so I finally got around to cracking some of these batteries open to try to get some SOCl₂ out. Here's a quick summary of the results:

1) The battery was fastened to a labstand inside of the fume hood. Two holes (about 1.3 mm thick) were drilled into the top of the battery (thinner holes caused liquid to spew out...). (A word of caution here. This suff is really super corrosive. Every time a drop landed on my nitrile glove it would actually seep through, which was pretty uncomfortable to say the least..)

2) The content was then drained into a cylinder. This was repeated for a total of six batteries. The colour of the liquid was a dark purple-black and was 40ml in total. So it definitely needs to be purified.

3) The empty batteries were submerged in mineral oil to keep the lithium in the batteries from reacting with moisture.

4) I tried to open one of the batteries using an iron saw, but this didn't really work since I didn't have anywhere to clamp the battery down. So I just ended up storing them in mineral oil.

5) One observation is that when the liquid in the batteries bubbled out or touched the sides of the funnel, a yellowish solid formed. This clearly still had some SOCl₂ in it, because washing it with water caused acidic fumes to evolve from it (unfortunately I realized this too late to also collect it). If anyone knows what this solid may be, then I'd be really curious to know.

6) The impure SOCl₂ from step 2) was purified by simple distillation (the boiling point of SOCl₂ is about 74.6^oC). I'm aware that there are more sophisticated methods for purifying this compound, but unfortunately they are not available to me.
Nonetheless, a translucent faintly yellow liquid was collected, while all the black stuff remained behind).

7) The total amount collected was exactly 30ml, corresponding to an average of 6ml/batter. The somewhat darker yellow than usual also indicates that the product isn't 100% (but to be honest, I don't think I've ever actually seen commercial SOCl₂), but I would guess that it's still mostly SOCl₂ since it fumed like crazy whenever it was poured into a new vessel.

Discussion

So first of all, is it worth it? I guess it depends on your application. I just want it to make some acyl halides, but if you want it of much larger experiments it's probably a bit of a hassle.

In terms of the cost, I saw that on a certain Chinese Amazon-like marketplace (which by the way has lots of wonderful and cheap reagents etc... btw), these batteries are sold for less than 10% of the price you pay on the other Amazon.
Also, if you manage to somehow get the lithium out them, then you have that too.

Also, as for safety equipment, as long as you're working in a well ventilated space and use plenty of gloves and ideally some kind of gas mask, you should be fine. I actually just rinsed the glassware in the sink and the resulting fumes were no problem.

Question: Since I probably won't be using the empty battery shells for their lithium and I also don't exactly want to dump unprotected lithium into the battery collection bin, might it be a "decent" idea to throw them into a barrel of water far away (in a safe area), wait for them to go WOOSH! and then collect the rest to through away properly?.

[Edited on 8-8-2021 by Monoamine]

Monoamine - 7-8-2021 at 18:37

Prepic - 7-8-2021 at 23:09

Very impressive Monoamine, love to see a guide on how to extract SOCl2 from batteries. I personally think accessibility to chemicals generally overweighs economic concerns at least when it comes to small scale experiments.

I think your solution to disposal will work well. In the recycling process, metal casing are also recycled.

Monoamine - 8-8-2021 at 10:49

Quote: Originally posted by Prepic

Very impressive Monoamine, love to see a guide on how to extract SOCl2 from batteries. I personally think accessibility to chemicals generally overweighs economic concerns at least when it comes to small scale experiments.

I think your solution to disposal will work well. In the recycling process, metal casing are also recycled.

Thanks for the tip regarding disposing of the lithium.

One thing I learned from this is also to use a very hard (possibly diamond tipped drill bit, since standard drill bit take ages to get through and I actually killed a few of them, probably since the SOCl₂ corroded them...)

Tdep - 8-8-2021 at 19:16

This worked so much better than I ever thought it would. Well done mate, very cool stuff. Great working having an idea and then seeing it through to trying it out!

karlos³ - 8-8-2021 at 19:17

Thats really interesting.
Can you give a rough calculation, without your working hours, what all that "fun" has cost you now, just the material itself?

I am actually quite surprised that these batteries as a source seem to be much more viable than I suspected them to be.

I will stil prefer buying it, but its very good to see someone figuring that out successfully in practice

teodor - 9-8-2021 at 03:23

"Also, as for safety equipment, as long as you're working in a well ventilated space and use plenty of gloves and ideally some kind of gas mask, you should be fine. I actually just rinsed the glassware in the sink and the resulting fumes were no problem."
You are not quite right, Monoamine, repeating again that the danger is associated with SOCl2 decomposition products, those HCl and SO2 fumes. The toxicity is connected with SOCl2 itself.
1. It is very volatile. Vapour pressure is 1/2 of acetone. There is not enough water vapour in the air to neutralise it.
2. The fumes are denser than air. Ventilation which can work well with most of other compound (let say, NO2, HCl or SO2) doesn't work well.
3. Usual gas mask with protection from "acid fumes" doesn't protect at the same level.
4. I red studies of SOBr2 toxic action but I think for SOCl2 it should be similar. When somebody breath its fumes he gets SOBr2 dissolved in fat.
So, I am glad you managed the process but I think you don't properly marked the dangers, making accents on decomposition products HCl and SO2. SOCl2 is much more toxic than any of them.

Also I can see you were working in a professional fume hood with baffles. Baffles are effective against dense fumes SOCl2. But I believe this element could be absent in many DIY fume hoods.

[Edited on 9-8-2021 by teodor]

Update

Monoamine - 9-8-2021 at 15:53

For the sake of safety I feel I have to give a quick update on later developments.
So, as I said, I put the empty battery shells under mineral oil so the lithium wouldn't react. I then tightly sealed the beaker with aluminum foil, which was probably my first mistake.

The next day when I went to where I stored it the air REEKED of HCl which was so acrid I couldn't even take the beaker outside without eye and lung protection. When I checked on it a few hours later the foil that had covered the beaker was completely gone. Guess I got lucky that the hydrogen gas this must have generated was all outdoors... The battery shells themselves were also super corroded...

On the one hand this is clearly a lesson to be more careful next time, but on the plus side it also means that there was obviously still a pretty large amount of SOCl₂ left in the batteries, so if you make sure to drain them completely you should be able to get a much better yield than me.

There was a question about cost. I don't remember exactly, but I think it was around 20sh a pop, which means I can't do this very often, but on the other hand, since Alibaba has them for around 4$ (and less for bulk orders), it will have to come from there in the future.

Also, an acid resistant metal saw would come in handy to be able to open them completely, but I don't know if there even is such think, haha.

Monoamine - 9-8-2021 at 16:01

Quote: Originally posted by teodor

"Also, as for safety equipment, as long as you're working in a well ventilated space and use plenty of gloves and ideally some kind of gas mask, you should be fine. I actually just rinsed the glassware in the sink and the resulting fumes were no problem."
You are not quite right, Monoamine, repeating again that the danger is associated with SOCl2 decomposition products, those HCl and SO2 fumes. The toxicity is connected with SOCl2 itself.
1. It is very volatile. Vapour pressure is 1/2 of acetone. There is not enough water vapour in the air to neutralise it.
2. The fumes are denser than air. Ventilation which can work well with most of other compound (let say, NO2, HCl or SO2) doesn't work well.
3. Usual gas mask with protection from "acid fumes" doesn't protect at the same level.
4. I red studies of SOBr2 toxic action but I think for SOCl2 it should be similar. When somebody breath its fumes he gets SOBr2 dissolved in fat.
So, I am glad you managed the process but I think you don't properly marked the dangers, making accents on decomposition products HCl and SO2. SOCl2 is much more toxic than any of them.

Also I can see you were working in a professional fume hood with baffles. Baffles are effective against dense fumes SOCl2. But I believe this element could be absent in many DIY fume hoods.

[Edited on 9-8-2021 by teodor]

TBH, I'm not sure how well this fume hood protects against acidic fumes, since it's ductless and uses filters. I think the ones in this one are more designed for hydrocarbons (but maybe filters designed to handle acids exist??) I'm also kind of tempted to try to build a DIY vent to minimize the risk of anything toxic floating around indoors. Project for a rainy day...

karlos³ - 9-8-2021 at 16:12

If its something corroding, that gives off HCl fumes or so, I put a layer of plastic foil in between, and then Al foil over this, to avoid direct exposure and it turn, Al crumbles falling into whatever is in the beaker.
Works fine.

Quote:

There was a question about cost. I don't remember exactly, but I think it was around 20sh a pop, which means I can't do this very often, but on the other hand, since Alibaba has them for around 4$ (and less for bulk orders), it will have to come from there in the future.

You mean "a pop", like in, per battery opened?

So it was over 120$ just for the batteries?

Wow.
Quite the expense for only 30ml of SOCl2!

I think I paid 18€ for 100ml or so ten years ago.

teodor - 10-8-2021 at 02:06

Quote: Originally posted by Monoamine

I didn't know that ductless fume hood are effective for this case but if you haven't troubles (like burning throat or hoarse voice after the experiment) your protection was probably OK.
Also probably you can modify any ductless fume hood and add an air exhaust line.
What I can confirm is that the exhaust line which collects the air only from a top of a hood is not enough to work with this compound, you have to draw air from the bottom, so if you plan to do work with SOCl2 design your hood draw line the same way as it is in your ductless hood.

Monoamine - 10-8-2021 at 06:39

Quote: Originally posted by karlos³

If its something corroding, that gives off HCl fumes or so, I put a layer of plastic foil in between, and then Al foil over this, to avoid direct exposure and it turn, Al crumbles falling into whatever is in the beaker.
Works fine.

Quote:

You mean "a pop", like in, per battery opened?

So it was over 120$ just for the batteries?

Wow.
Quite the expense for only 30ml of SOCl2!

I think I paid 18€ for 100ml or so ten years ago.

Yea definitely an experiment I won't be able to repeat at that cost. If I do it again I'll definitely order from Alibaba. Still not as good as store-bought, but sadly I haven't found one that sells it to private individuals...