The Bucket Cell - Start to Finish

[TomasBrod]

A year ago I built and successfuly run a Na chlorate cell with gouging rods graphite anodes. I did not produce much, but I gathered valuable experience.

 

First, erosion of graphite is not as big problem as corrosion of copper wire connection to the electrode. Despite the connection being sealed with molten wax, chlorine gas found its way to copper through the porous grphite.

 

Second, I developed an easy way to extract large (3-6mm) chlorate crystals from the cell liquor. I ran the cell always saturated with sodium chloride

and peridically added loose crystals of chloride to the bottom every few days. When the solid crystals did no longer dissolve after few days of runtime,

I knew the cell liquor was saturated with both chloride and chlorate.

To get rid of suspended carbon particles I let the liquor settle idle for two days and decanted clear liquid. Then I put the liquor in a fridge-freezer overnight to decrease temperature. In the morning I could extract nice crop of large chlorate crystals with a kitchen strainer. The next run (with recycled liquor topped with chloride sol.) yelded sightly more crystals.

This is due to large variance of solubility NaClO₃ in respect to temperature, while sodium chloride solubility desnt change (much).

 

Also my first post, so ... Hello

[WSM]

A year ago I built and successfuly run a Na chlorate cell with gouging rods graphite anodes. I did not produce much, but I gathered valuable experience.

First, erosion of graphite is not as big problem as corrosion of copper wire connection to the electrode. Despite the connection being sealed with molten wax, chlorine gas found its way to copper through the porous grphite.

Second, I developed an easy way to extract large (3-6mm) chlorate crystals from the cell liquor. I ran the cell always saturated with sodium chloride

and peridically added loose crystals of chloride to the bottom every few days. When the solid crystals did no longer dissolve after few days of runtime,

I knew the cell liquor was saturated with both chloride and chlorate.

To get rid of suspended carbon particles I let the liquor settle idle for two days and decanted clear liquid. Then I put the liquor in a fridge-freezer overnight to decrease temperature. In the morning I could extract nice crop of large chlorate crystals with a kitchen strainer. The next run (with recycled liquor topped with chloride sol.) yelded sightly more crystals.

This is due to large variance of solubility NaClO₃ in respect to temperature, while sodium chloride solubility desnt change (much).

Also my first post, so ... Hello

 

Hi TomasBrod.

 

Welcome to the discussion. Thanks for the description of your system and your experiences with it. Your story is like so many others here, we start simply and learn, step by step till we are either satisfied with our level of accomplishment or continually modify our approach, constantly working at optimizing our system (I think I fall into the latter category).

 

We are all at different levels of proficiency, but most are willing to help by sharing what we've learned. If you have questions, feel free to ask. Someone here will usually answer, and often several will add to the discussion till it's well covered.

 

WSM

[TomasBrod]

Hi TomasBrod.

Welcome to the discussion.

Thank you, wsm.

 

You may be able to just continuously add solid sodium chloride to the running cell, along with the standard HCl adjustments and perhaps topping up with water and eventually just start crystallizing out chlorate just like in a potassium cell.

I just want to confirm that the method Mumbes proposed works. Maybe I should have phased my first post better.

So If anyone wants Na chlorate, just put your liquor in the freezer and don't forget to recharge with chloride afterwards.

It was mentioned on on Alan Yates site too IIRC.

 

According to the solubility graphs on the oxidizing/chlorate site, it is possible to salt out na chlorate, but you would need to know

concentration of your solution and precise measurements. I was not able to do it.

 

Recently I managed to produce good looking GSLD (with acetates) anode and can't to try it out. Should I start new thread for that?

[schroedinger]

What is a GSLD anode?

[Arthur]

Graphite Substrate Lead Dioxide

 

Supposedly it's the only material that will go through from chloride to perchlorate in one go, as yet they are too hard to make for there to be a reasonable body of current knowledge on them.

[schroedinger]

Ok, never that them written like that. LD on Ti also goes from chloride to perc, same goes for platinum. The graphite anodes have some disadvantages (if the ld brakes no passivation, witch can be a problem, since graphite erodes fast during the formation of perc). But graphite is a good conductor.

But there could be an other anode that maybe is much more interesting, glassy carbon. In industry it gets used in persulfate cells, with else need to run with LD or platinum, for the same reasons as in a perc cell.

 

If i remember right they use quite high current density of 20 A/cm^2. I always wanted to that, but nevee came across such an anode at a decent price.

Edited May 20, 2016 by schroedinger

[WSM]

Thank you, wsm.

I just want to confirm that the method Mumbes proposed works. Maybe I should have phased my first post better.

So If anyone wants Na chlorate, just put your liquor in the freezer and don't forget to recharge with chloride afterwards.

It was mentioned on on Alan Yates site too IIRC.

According to the solubility graphs on the oxidizing/chlorate site, it is possible to salt out na chlorate, but you would need to know

concentration of your solution and precise measurements. I was not able to do it.

Recently I managed to produce good looking GSLD (with acetates) anode and can't to try it out. Should I start new thread for that?

 

You could, but it would work here; or better yet, In the potassium (per)chlorate thread. It's your choice. It sounds interesting.

 

WSM

[Mumbles]

Thank you, wsm.

 

I just want to confirm that the method Mumbes proposed works. Maybe I should have phased my first post better.

So If anyone wants Na chlorate, just put your liquor in the freezer and don't forget to recharge with chloride afterwards.

It was mentioned on on Alan Yates site too IIRC.

 

According to the solubility graphs on the oxidizing/chlorate site, it is possible to salt out na chlorate, but you would need to know

concentration of your solution and precise measurements. I was not able to do it.

 

Recently I managed to produce good looking GSLD (with acetates) anode and can't to try it out. Should I start new thread for that?

 

 

Glad to know I'm not always talking out of my rear end. I suspect there is an easier way to at least ball park the chlorate to chloride ratio. One reference I posted the other day mentioned specific gravity in relation to the composition. There may also be a way to do it via conductivity.

[schroedinger]

Should I start new thread for that?

Or a blog entry, which we can connect to the (per) chlorate thread, so it is easy to find in the 170 sites.

 

@mumbles:

If you assume that the cell liquor will always be saturated, it should be enough to determine how much chloride is in the liquor, which is done fast with silver nitrate.

Edited May 20, 2016 by schroedinger

[WSM]

I was trying to find a solubility graph for mixtures of sodium chlorate and sodium chloride. I was curious as to whether you can "salt out" sodium chlorate by adding sodium chloride. Sodium chloride has very little solubility change over the temperature range we deal with in these cells. I came across a few references of interest, which you may have seen before. It seems like if you know the general composition of your cell liquor, you can add a measured amount of NaCl and collect the crystallized chlorate. By following the solubility curve, you can preferentially isolate the chlorate. You may be able to just continuously add solid sodium chloride to the running cell, along with the standard HCl adjustments and perhaps topping up with water and eventually just start crystallizing out chlorate just like in a potassium cell. Once you have an appreciable amount turning off the cell and allowing it to cool should yield even more.

Alternatively, if you're looking for an electrolyte liquor for perchlorate, you may be able to just top up a few times with chloride until you begin to approach saturation to allow for the maximum amount of chlorate percursor. I'm not sure that we'll ever be able to get a low enough chloride content for the electrodes to not be attacked using a pseudo-one pot setup. I know it's more work, but it would seem ideal to isolate the chlorate before moving on to perchlorate. By "salting out" the chlorate from the cell, you may just be able to use the precipitate. I'm far from an expert on this sort of thing, but it sounded like even if all the chloride doesn't initially dissolve that it will be brought back into solution as more chlorate is produced.

https://books.google.com/books?id=_R00NqWST6MC&pg=PA167&lpg=PA167&dq=Co-solubility+of+sodium+chloride+and+sodium+chlorate&source=bl&ots=u8X2IiDujU&sig=iAqgR_9MYor9YZ6izPpBQorGsiA&hl=en&sa=X&ved=0ahUKEwj73KWQueHMAhVEez4KHQZ3CzsQ6AEIQDAG#v=onepage&q=Co-solubility%20of%20sodium%20chloride%20and%20sodium%20chlorate&f=false

http://www.oocities.org/capecanaveral/campus/5361/chlorate/akagraph.html

 

Hi Mumbles,

 

This post is very insightful and follows my thinking in the development of my sodium experiment. I've arranged my sodium chlorate cell with a pump and various valves so I have at least three options:

1. run the cell without fluid flow, like a batch system or a bucket cell
2. run the cell with fluid circulation from the bottom of the cell to the top using the pump
3. run the cell (as in 2.) but pump through the salt reservoir, to recharge the chloride as it's consumed

A fourth option is to vary the three options in any combination as the cell runs, depending on observed cell conditions. I'm also considering methods to observe and monitor the specific gravity of the electrolyte as the cell runs, noting variations during different stages of the run.

 

The difference between my sodium experiment and most others is my setup is dynamic, rather than static (with pumps moving the electrolyte actively and not passively, as in a batch system). This might work extremely well; we'll see...

 

There's a lot to learn, and I think this setup will afford me the opportunity to dial in a workable process of sodium chlorate manufacture and purification.

 

Thanks again, for your input. The ideas you and Arthur (plus many others, here) have presented, have inspired me to develop this system to test the theories.

 

WSM

[pyrojig]

Wsm :

Have you found the specific Gravity method to be viable for a sodium sys? or is it null and void due to the solubility of both salts? Im sure it will have a wonderfull application in the kclo3 cells.

Btw Thank you for spending time to blaze a trail in (per) chlorate production ( on a advanced amateur scale) . I would be more inclined to contribute to the research , but work load has been overwhelming . I hope to get a grasp on that ,and jump in to the research and findings with you guys soon.

[WSM]

Wsm :

Have you found the specific Gravity method to be viable for a sodium sys? or is it null and void due to the solubility of both salts? Im sure it will have a wonderfull application in the kclo3 cells.

Btw Thank you for spending time to blaze a trail in (per) chlorate production ( on a advanced amateur scale) . I would be more inclined to contribute to the research , but work load has been overwhelming . I hope to get a grasp on that ,and jump in to the research and findings with you guys soon.

 

So far, no. The specific gravity doesn't change enough between NaCl and NaClO₃ solutions for S.G. measurements to indicate an "end-of-run" point with any degree of accuracy. Other measurements may do that, but I haven't discovered them yet.

 

Yes, S.G. is excellent for showing the "end-of-run" point in potassium chlorate cells. This is because the potassium chlorate, being so much less soluble in saturated electrolyte that it drops out as crystals, changing the S.G. as the chloride is used up and the chlorate precipitates out of the solution. So far, in the sodium system, it's beginning to appear that we're working toward having a constantly saturated solution of chloride and chlorate before chlorate crystals will appear; so the specific gravity isn't expected to change enough to be useful as an indicator.

 

Too bad, it would have been nice if it worked. Apparently, it works very well in potassium chlorate systems (two fellow electrochemists use it constantly for potassium chlorate, running at high CE by using pH control).

 

You're welcome, and thanks for the encouragement. This is all new territory for me and an interesting experiment, but so far, so good. I'm able to overcome obstacles and road blocks as I encounter them, so far; and push on. I hope I can successfully create a large supply of sodium chlorate to experiment with.

 

Good luck with your work. I hope you can get to the point where you have more free time and still be able to support your family, comfortably.

 

WSM

Edited June 4, 2016 by WSM

[WSM]

Recently I managed to produce good looking GSLD (with acetates) anode and can't to try it out.

 

Hopefully it's a good working anode, too! I'd like to know more about the process you used. If you get a chance, please share your method. Thanks.

 

If I had a good, stabile GSLD anode, I'd be inclined to try the sodium chloride to sodium perchlorate system alluded to by many here. They're likely referring to an article published by researchers in India several decades ago, where they set up a smaller and a larger pilot plant using GSLD anodes that they made and succeeded in making a respectable amount of sodium perchlorate with them (a proof of concept experiment, if you will).

 

I look forward to hearing more about your LD on graphite anode, and the process to make them.

 

WSM

Edited July 30, 2016 by WSM

[TomasBrod]

Hopefully it's a good working anode, too! I'd like to know more about the process you used. If you get a chance, please share your method. Thanks.

 

I want to save the electrode for perchlorate and currently i have very little sodium chlorate left.

It looks like the coating may be too thin for it to work, idk.

 

The process:

 

Vinegar 5% (clear with yellow tint) added to Lead(II,IV) oxide and some scrap copper from wires and gouging rods.

Reaction progressed slowly. I let it react until distinct acidic smell vanished and the solution turned blue. I belive copper and the lead oxide produced some electric current that oxidised the copper and reduced the oxide. I tested for lead with NaHCO3 -> white precipitate.

The electrolysis was performed in small bottle (mistake) just enough to hold the carbon rod which was 12cm submerged and 1.5cm dia and two copper wires as cathodes. Current was kept low aout 80mA just in case. During the electrolysis the hard blue slowly faded to clear. Occasionally I shaked copper deposits of the cathodes to avoid short circuit but short occurred anyway in the bottom so I then replaced half of the electrolyte with fresh solution and removed the deposits. Second time the blue disappeared I had no more to replace and bubbles started to form on anode and lead on cathodes so I stopped the experiment. This was all done over two days.

Two interesting things happened: brown than black see-trough micro-layer appeared on the surface of solution spreading from the anode (i suspect PbO2), second the copper deposit turned into very fine powder.

The coating is real shiny like glass and bumpy-smooth. There is a rainbow where the coating ends.

This experiment showed that copper salts are necessary and larger container with more volume would be better.

I am bit scared of the poisonous lead salts.

I am going to repeat with better measurements and preparations someday (in a new thread I promise).

[WSM]

I want to save the electrode for perchlorate and currently i have very little sodium chlorate left.

It looks like the coating may be too thin for it to work, idk.

The process:

Vinegar 5% (clear with yellow tint) added to Lead(II,IV) oxide and some scrap copper from wires and gouging rods.

Reaction progressed slowly. I let it react until distinct acidic smell vanished and the solution turned blue. I belive copper and the lead oxide produced some electric current that oxidised the copper and reduced the oxide. I tested for lead with NaHCO3 -> white precipitate.

The electrolysis was performed in small bottle (mistake) just enough to hold the carbon rod which was 12cm submerged and 1.5cm dia and two copper wires as cathodes. Current was kept low aout 80mA just in case. During the electrolysis the hard blue slowly faded to clear. Occasionally I shaked copper deposits of the cathodes to avoid short circuit but short occurred anyway in the bottom so I then replaced half of the electrolyte with fresh solution and removed the deposits. Second time the blue disappeared I had no more to replace and bubbles started to form on anode and lead on cathodes so I stopped the experiment. This was all done over two days.

Two interesting things happened: brown than black see-trough micro-layer appeared on the surface of solution spreading from the anode (i suspect PbO2), second the copper deposit turned into very fine powder.

The coating is real shiny like glass and bumpy-smooth. There is a rainbow where the coating ends.

This experiment showed that copper salts are necessary and larger container with more volume would be better.

I am bit scared of the poisonous lead salts.

I am going to repeat with better measurements and preparations someday (in a new thread I promise).

 

Hi TomasBrod,

 

This is very interesting. I like the looks of your anode and wonder how well (or if) it'll work the way we hope it will. If the process proves as effective as it appears to, some minor refinements will improve the efficiency (as well as make the availability of GSLD to amateurs a reality). Very cool!

 

I'm guessing the best method of attaching power to the anode is above the electrolyte (and maybe above the cell lid, and through a compression fitting). I'm getting ahead of myself, first we have to get the well-made GSLD anodes; and then worry about the particulars of setting up a cell.

 

Do you have the reference material that inspired your attempt? That would be an interesting read.

 

Thanks for sharing your work.

 

WSM

[WSM]

The sodium chlorate experiment is working well and I'm learning a lot. I think it'll work in a bucket cell too, but the precaution of putting the bucket in a large plastic pan for containment would be wise (in case the bucket fails).

 

So far, I've harvested about 5 kilos (roughly 11 pounds) of sodium chlorate crystals from the first run. I think the second run (which I plan to start after the PGI Convention) with recharged electrolyte will produce more chlorate in less time because of the precursors in the depleted liquor. We'll see...

 

I'm certain a bucket cell would work admirably for the next step of turning sodium chlorate into sodium perchlorate. Once I have a large stock of NaClO₃ to work with, I'll have to make up the electrolyte and try it.

 

This is getting really fun!

 

WSM

Edited August 1, 2016 by WSM

[TomasBrod]

Do you have the reference material that inspired your attempt? That would be an interesting read.

I have read lot on this topic, like science-madness, Swede'đ article, but the first inspiration came

from this post on instructables not much but it has all the key points

then research on how do I get my (solid) lead dissolved

then I was sidetracked by copper acetate crystals for a while.

[WSM]

I have read lot on this topic, like science-madness, Swede'đ article, but the first inspiration came

from this post on instructables not much but it has all the key points

then research on how do I get my (solid) lead dissolved

then I was sidetracked by copper acetate crystals for a while.

 

Thanks, TomasBrod.

 

That looks interesting and worth a try. Please let us know how they work and hold up when you get some NaClO₃ and try them out. I may try my hand at making some GSLD anodes at some point in the future, and this information helps.

 

WSM

[WSM]

Introducing - The Bucket Tank

In an effort to simplify the process of making home made oxidizers, and because of the universal availability of 5 gallon (+- 20 liter) buckets, Swede promoted the idea of the bucket cell. The main requirement was a bucket cell adapter (or BCA) to make this all possible.

Swede was on to something.

This morning, I was pondering about making a mixing tank from a standard 5 gallon bucket with a lid, and where I might apply one or more bulkhead adapters for plumbing pipe-work into and out of the bucket tank.

I considered that the bulkhead adapters are best suited to a flat surface and how I might be able to use them on the rounded sides of a bucket, when it came to me to mount them to the bottom of the bucket and the lid (which are mostly flat, obviously).

This would require making a standoff base for the bucket, but that would be easy with pressure treated 2x4 lumber and deck grade screws. The whole assembly could be set up in a plastic concrete-mixing tub as a secondary containment in case of a failure of the bucket. The best part, most of the materials can be found at the nearest "Big Box" home center or hardware store. I found the bulkhead adapters on eBay for about $3.50 each in sets of 4, with free delivery.

I believe this will be a viable option for a number of wet processes, including brine preparation and purifying. The possibilities are limited only by the imagination of the builder and the quality of the materials used.

If anyone needs more information or clarification of the details, feel free to ask here and one or more of us can offer suggestions.

WSM

Bucket Tank Concept.doc

Edited August 30, 2016 by WSM

[OldMarine]

An irrigation valve box makes an excellent bucket stand with pre-cut pipe access ports. A bead of silicone around the rim makes a very sturdy stand:

 

 

 

[WSM]

An irrigation valve box makes an excellent bucket stand with pre-cut pipe access ports. A bead of silicone around the rim makes a very sturdy stand:

Bucket Stand.jpg

 

Now that's slick. Thanks OldMarine, I like it (it's certainly easier than building something up from scratch). An excellent suggestion.

 

WSM

[WSM]

An irrigation valve box makes an excellent bucket stand with pre-cut pipe access ports. A bead of silicone around the rim makes a very sturdy stand:

Bucket Stand.jpg

 

Hey, I like that folding table with a sink built in. You've got a nice setup for outdoor activities. Add in a propane fired pizza oven and you could have the Mother of all Summer pizza parties (call me if you do )!

 

Thanks again for the tip (I see I need to get back to Home Depot soon).

 

WSM

Edited August 28, 2016 by WSM

[WSM]

An irrigation valve box makes an excellent bucket stand with pre-cut pipe access ports. A bead of silicone around the rim makes a very sturdy stand:

Bucket Stand.jpg

 

Okay, I've gotten a valve box and have several buckets to choose from; I'll see if I can assemble the parts with some PVC bulkhead adapters to make a mixing tank and/or a holding tank for purified brine (or any number of other liquid handling purposes I can dream up). I'll show photos of the assembled Bucket Tank when I get it made up.

 

Many thanks to OldMarine for the suggested setup.

 

WSM

Edited September 4, 2016 by WSM

[WSM]

Okay, I've gotten a valve box and have several buckets to choose from; I'll see if I can assemble the parts with some PVC bulkhead adapters to make a mixing tank and/or a holding tank for purified brine (or any number of other liquid handling purposes I can dream up). I'll show photos of the assembled Bucket Tank when I get it made up.

Many thanks to OldMarine for the suggested setup.

WSM

 

I've gotten started on assembling the bucket tank and have a few photos:

 

 

The two containers are glued together with silicone sealer (or something similar), inside and out:

 

 

I bored a hole to mount the bulkhead adapter:

 

 

I plan to add other fittings, specific to the application I plan to use the tank for. I'll show more photos as the preparation continues.

 

WSM

[WSM]

To use the bucket tank for a brine preparation tank, I see the need to put an inlet filter in the opening of the bulkhead adaptor mounted in the bottom of the bucket. Because of the nature of the solutions used, metal fittings are out of the question. After looking locally for polymer filter fittings and being dissatisfied with what I saw, I've determined to fabricate my own.

 

The bulkhead adaptors have 3/4" NPS (National Pipe Straight) threads running through the center, so I started with a grey, 6" PVC 3/4" nipple. I cut the nipple into two 3" lengths with NPT (National Pipe Taper) threads on one end. The other end is a clean cut, flat edge since I used a parting tool on my lathe to do the job.

 

After deburring the flat end, I used grey CPVC cement and apply a good amount to the flat ends of the half nipples. I placed them on a remnant of 1/8" thick grey PVC plate stock I had on hand. After it dried for a day, the bond is permanent.

 

 

I then cut the pieces apart and turned the pipe sections on the lathe to clean up the sealed end, with a slight, rounded chamfer on the sealed outer edge. After the ends are cleaned up, I still need to drill lots of tiny holes in the sealed pipe to form my filters.

 

The whole point (in this application) is to keep the salt crystals in the tank, but circulate the water/brine solution through the crystals to concentrate the brine. The filter also helps prevent coarse contaminants from entering the pump.

 

I'll try this out in the bucket tank and see how it works.

 

More later...

 

WSM

Edited September 9, 2016 by WSM