making potassium (per) chlorate

[OldMarine]

Thanks for giving us something pyro to read rather than news!

[WSM]

Thanks for giving us something pyro to read rather than news!

 

You bet. You're welcome.

 

WSM

[WSM]

I wonder at times whether my system is too conservative. The electrodes are larger than I've used before (for more than a few minutes of testing), but the RC (reaction chamber) is much bigger, and holds more electrolyte than any cell I've run to date, by about five times (not counting my first failed bucket cell).

 

The problem is, if I make the electrodes larger, the heating can quickly become a serious issue, requiring active water cooling, or some other extreme measure. It's not that I'm unable or unwilling to do so; but I haven't seen this experiment I'm currently working on through, yet. There's so much we don't have a handle on, and I think I need the experience I'm gaining now before I go on to explore a more radical approach.

 

The system plods along, and I'm logging several points of data as it progresses (volts, amps, temperature, mode of operation, time and date, plus hour of operation). I'm encouraged to also log the specific gravity (S.G.) and pH, which I may add in before long. All this data will help determine the progress of the system and the efficiency, too, if all goes well.

 

I'll keep everyone up to date as things continue.

 

WSM

[Arthur]

The advantage of a big cell (relative to the current applied) is that changes happen slowly so half a day at work or time sleeping shouldn't cause immediate dramatic problems, more like steady changes.

[WSM]

The advantage of a big cell (relative to the current applied) is that changes happen slowly so half a day at work or time sleeping shouldn't cause immediate dramatic problems, more like steady changes.

 

That's a very good point, Arthur. Since I'm still gainfully employed outside the home, it's comforting that the cell runs steadily while I'm away for so many hours per day.

 

I'm so used to the quick turnaround on smaller potassium chlorate cells that the slow pace of this sodium chlorate experiment is a bit frustrating. I need to be calm, patient, and learn the lessons this system has to teach me.

 

Thanks for the support and encouragement.

 

WSM

Edited June 14, 2016 by WSM

[WSM]

Yesterday I read something in Wikipedia that has me wondering about my approach to making sodium chlorate. It brings up the question if pH has a greater part in making the precursors go to chlorate or will stay as hypochlorite/hypochlorous ions.

 

The possibility exists that chlorate being formed in one part of the cell is also breaking down in another part of the cell as the system runs. It's been suggested that by either the addition of dichromates or maintaining the correct pH, you can prevent the breakdown of chlorates as they're formed and encourage the precursors to go to completion as chlorates.

 

I need to study this further. I may decide to add in pH control sooner than originally planned if this is found to be true. I'm starting to think it's possible that with potassium chlorate manufacture pH control is recommended and in sodium chlorate manufacture pH control may be required.

 

We'll see...

 

WSM

[TomasBrod]

I've been looking for MMO (or PbO2) electrodes since New year and I coud not find anything less than 40€ (incl.shipp.).
Recently I discovered a bunch of Bleidioxid, MMO, Perchlorat, Chlorat, HHO, Platinelektrode
(and other similar) electrodes from Germany on e-bay. It is not clear from the name or description what is the coating.
The price is not bargain so I am asking: Is it worth it? Are they suitable for chlorate (and if pbo2 eventually for perchlorate) production?

I'm starting to think it's possible that with potassium chlorate manufacture pH control is recommended and in sodium chlorate manufacture pH control may be required.

According to my experiments, pH control is not required. However CE will suffer as everyone says.

Edited June 15, 2016 by TomasBrod

[WSM]

I've been looking for MMO (or PbO2) electrodes since New year and I coud not find anything less than 40€ (incl.shipp.).

Recently I discovered a bunch of Bleidioxid, MMO, Perchlorat, Chlorat, HHO, Platinelektrode

(and other similar) electrodes from Germany on e-bay. It is not clear from the name or description what is the coating.

The price is not bargain so I am asking: Is it worth it? Are they suitable for chlorate (and if pbo2 eventually for perchlorate) production?

According to my experiments, pH control is not required. However CE will suffer as everyone says.

From the photo it looks like the LD on titanium anode patsroom was selling years ago. The other clue is "bleidioxid", the old German word for lead (Pb) is blei and obviously "dioxid" is dioxide. At 100 mm by 100 mm, the anode would require 40 amps if applying 0.2 A per cm² using two cathodes.

 

I'd save an anode like that for perchlorate production and use MMO for chlorate.

 

WSM

Edited June 16, 2016 by WSM

[taiwanluthiers]

The price they are asking for that anode (when it's that Chinese stuff) is just horrendous. They are likely capitalizing on the explosive precursor laws in the EU. At that price you are better off using platinum.

 

There was someone else selling it at a more reasonable price but they have not sold it for years now.

 

Where can you get that Chinese anode from the source? Who sells them and what are they originally used for?

[WSM]

The price they are asking for that anode (when it's that Chinese stuff) is just horrendous. They are likely capitalizing on the explosive precursor laws in the EU. At that price you are better off using platinum.

There was someone else selling it at a more reasonable price but they have not sold it for years now.

Where can you get that Chinese anode from the source? Who sells them and what are they originally used for?

 

Even patsroom was selling them for $55 US several years ago (the US equivalent price for the German one is $72.85 with free shipping; not that different, really).

 

If we could get the LD anodes in bulk from China on a co-op order, I'm sure the savings would be considerable; but delivery to many participants in several different countries would eat up the savings very quickly.

 

WSM

Edited June 16, 2016 by WSM

[WSM]

According to my experiments, pH control is not required. However CE will suffer as everyone says.

 

Did you track the amp/hours of your runs? How many amp/hours per liter of electrolyte in your cell (plus how much sodium chlorate was the yield of your setup?)? Any details we can use for comparison?

 

WSM

[taiwanluthiers]

The 70 dollar one is very small, maybe 2" x 3". The 10cm x 10cm one is considerably more, about 90 dollars.

[TomasBrod]

The other clue is "bleidioxid", the old German word for lead (Pb) is blei and obviously "dioxid" is dioxide.

It is clear now, I've got the descriptions mixed up. The description clearly states that one is PbO2 on Ti.

I'd save an anode like that for perchlorate production and use MMO for chlorate.

If I only could find MMO cheaper than PbO2 with the strip attached, because I am unable to attach one myself due to lack of welder. Otherwise I would already bought the mesh, which I saw many times and be happy.

Did you track the amp/hours of your runs? How many amp/hours per liter of electrolyte in your cell (plus how much sodium chlorate was the yield of your setup?)? Any details we can use for comparison?

No, sorry. I don't have any quantitative data. Other than I run it with six len=15cm dia=13mm gouging rods in circle around single steel/iron idk sheet shaped like tube cathode at I=3.5A in little over half liter of electrolyte.

 

 

[WSM]

It is clear now, I've got the descriptions mixed up. The description clearly states that one is PbO2 on Ti.

If I only could find MMO cheaper than PbO2 with the strip attached, because I am unable to attach one myself due to lack of welder. Otherwise I would already bought the mesh, which I saw many times and be happy.

No, sorry. I don't have any quantitative data. Other than I run it with six len=15cm dia=13mm gouging rods in circle around single steel/iron idk sheet shaped like tube cathode at I=3.5A in little over half liter of electrolyte.

 

How long did you run the cell and how much sodium chlorate did it yield?

 

Did you recharge the depleted liquor with more NaCl? How many times?

 

These details help us to understand how well it worked. Thanks.

 

WSM

[WSM]

The 70 dollar one is very small, maybe 2" x 3". The 10cm x 10cm one is considerably more, about 90 dollars.

 

You're right, that's not a very good deal. I suppose I'd have seen that if I could read German.

 

WSM

[WSM]

It is clear now, I've got the descriptions mixed up. The description clearly states that one is PbO2 on Ti.

If I only could find MMO cheaper than PbO2 with the strip attached, because I am unable to attach one myself due to lack of welder. Otherwise I would already bought the mesh, which I saw many times and be happy.

If the MMO anode is long enough, you could attach the power cord using a bolt and nut above the electrolyte, and on the cathodes, too. It's tricky but can be done.

 

I wonder if a welding shop can spot weld a strap or rod of CP titanium to the MMO anode for you? You never know unless you ask...

 

WSM

Edited June 16, 2016 by WSM

[taiwanluthiers]

It would be a tall order because very few know how to weld titanium and would balk at it.

 

Problem with Ti is it's rare enough that the only way to obtain it is mail order, let alone finding someone local who knows how to deal with it.

[WSM]

It would be a tall order because very few know how to weld titanium and would balk at it.

Problem with Ti is it's rare enough that the only way to obtain it is mail order, let alone finding someone local who knows how to deal with it.

 

You can TIG weld CP titanium while using a CP titanium filler rod. The filler rod is available, but probably special order.

 

Resistance welding (i.e., spot welding) works well, and some welding shops may be equipped to do it, but you have to ask.

 

WSM

Edited June 17, 2016 by WSM

[Arthur]

Swede published his plans for a DIY spot welder using a transformer from a microwave oven -suitably rewound. There are lots of examples on youtube.

 

MMO on CP Ti mesh is available online.

[TomasBrod]

How long did you run the cell and how much sodium chlorate did it yield?

 

Did you recharge the depleted liquor with more NaCl? How many times?

 

These details help us to understand how well it worked. Thanks.

I am sorry to disappoint you, but the data are simply not available. I did not keep records.

I recharged the cell many times. It was running 5 daynights then a day to settle carbon micro-particles and overnight in freezer. and repeat

I've got some C rods left and can buy more so I will probably set up another run in july. Hardest part are the connections: i am using candlewax to seal it, but the copper keeps disintegrating.

Swede published his plans for a DIY spot welder using a transformer from a microwave oven -suitably rewound. There are lots of examples on youtube.

 

MMO on CP Ti mesh is available online.

I thought about this. MOT is a gateway to some amazing experiments with high voltage or high current that would probably keep me away from pyro/chem for a long time.

 

I thought about plating some PbO2 or MnO2 but to mail order myself a titanium substrate + chemicals + chance to fail would overprice the current offers.

 

The amateur chemist is constantly temporary closed. I guess I just have to watch ebay and friends until something pops up (50€ is my limit).

Thanks for the suggestions WSM, Arthur, luthiers.

[taiwanluthiers]

If you could get the chemicals to make LD anode, you can get perchlorate.

 

Either that or be content with chlorate and learn to work around it. Good looking stars can be made for it but I have found chlorate stars tend to burn too fast.

[Arthur]

Currently my understanding is;

 

MMO on Ti is good for chlorate production but doesn't go to perc

 

PbO2 on graphite will go straight through from chloride to perc -but the electrodes are not commercially available and must be made in lab.

 

PbO2 on metal is available from China for silly money

 

Smooth surface platinum is the "old faithful" electrode for a cell from chlorate to perc -again lots of money.

[WSM]

I am sorry to disappoint you, but the data are simply not available. I did not keep records.

I recharged the cell many times. It was running 5 daynights then a day to settle carbon micro-particles and overnight in freezer. and repeat

I've got some C rods left and can buy more so I will probably set up another run in july. Hardest part are the connections: i am using candlewax to seal it, but the copper keeps disintegrating.

I thought about this. MOT is a gateway to some amazing experiments with high voltage or high current that would probably keep me away from pyro/chem for a long time.

 

I thought about plating some PbO2 or MnO2 but to mail order myself a titanium substrate + chemicals + chance to fail would overprice the current offers.

 

The amateur chemist is constantly temporary closed. I guess I just have to watch ebay and friends until something pops up (50€ is my limit).

Thanks for the suggestions WSM, Arthur, luthiers.

 

Too bad, that information could have been useful (hindsight is always 20:20).

 

I agree about the MOT and getting sidetracked on other projects (it happens to me all too often).

 

Plating your own LD (successfully) is not trivial, and it involves so much more than just acquiring the chemicals. Certainly I'd rather buy it than make it.

 

If one supplier doesn't have what you want or is temporarily out of stock, don't worry. Patience often wins out in the long run if you're persistent. Keep looking and keep your eyes open, and you'll usually find what you're looking for if you just don't give up.

 

Good luck.

 

WSM

Edited June 18, 2016 by WSM

[WSM]

Currently my understanding is;

1. MMO on Ti is good for chlorate production but doesn't go to perc
2. PbO2 on graphite will go straight through from chloride to perc -but the electrodes are not commercially available and must be made in lab.
3. PbO2 on metal is available from China for silly money
4. Smooth surface platinum is the "old faithful" electrode for a cell from chlorate to perc -again lots of money.

 

1. I agree.
2. PbO₂ on graphite may go straight through from chloride to perchlorate; but the conditions have to be right. I think they can be found commercially made, we just haven't found them yet (at an affordable price and quantity).
3. I think the PbO₂ on CP titanium anodes from China can be had for reasonable prices, but getting them here (wherever you live) can be expensive. Usually better prices are available when you buy in bulk. The problem is none of us want (or need) to sit on 100 of them, let alone tie up that much money in a hobby venture.
4. True. It works, but how long will it last, and at what cost?

 

WSM

Edited June 18, 2016 by WSM

[WSM]

If you could get the chemicals to make LD anode, you can get perchlorate.

Either that or be content with chlorate and learn to work around it. Good looking stars can be made for it but I have found chlorate stars tend to burn too fast.

 

There are methods and techniques to slow the burn of fast stars without compromising the other good features of them. This problem can probably be solved with developed skill and good judgement.

 

I certainly agree about fast burning chlorate stars, especially blues, but something as simple as changing the component ratios or color donors can have a dramatic effect on star burning speed.

 

Good and well-made chlorate stars have some wonderful features that can't be matched by comparable perchlorate formulations.

 

WSM