My easy way of making K perchlorate

[WSM]

Silver is not only the best electrical conductor but a hard metal, chemically very resistant does not rusted. A quality precious metal base Cu, Nb, Ti, it will not bring that quality. With such an expensive electrode, it is not worth the risk poor conductivity, poor quality base. The copper completely erodes in a chlorate perchlorate cell atmosphere. Titanium have poor conductivity. The electrode are tested and working in the long term with the specified parameters.

 

Interesting.

 

I nearly forgot about a sample anode material I got early on that showed great promise but had an issue during my first attempt to use it. This was an 1/8" (~3mm) OD wire that was MMO coated niobium with a copper core. The copper was large in diameter with a thin niobium layer coated with MMO.

 

The problem I encountered was in using a straight piece of the wire for an anode, with an epoxy bulb on the end of it to protect the exposed Nb and Cu of the anode wire. The epoxy failed and the copper was etched out of a portion of the anode.

 

It occurs to me now that if I had used a U shaped loop of that electrode material, where the ends were outside the cell, it probably would have worked well!

 

Since that time, I have obtained several pieces of MMO on CP titanium mesh, which have, and do work extremely well for chlorate production, I never looked back at that sample of MMO on niobium clad copper wire anode material I received all those years ago.

 

I still have it, by the way. I may have to do some small experiments with it to satisfy my curiosity, at some future time .

 

WSM

Edited April 22, 2022 by WSM

[Arthur]

MMO is the perfect anode for chlorate cells but it will not produce perc. Platinum is the best anode for perc -run carefully to avoid erosion, otherwise lead dioxide is suitable and sometimes ebay can supply.

[WSM]

Silver is not only the best electrical conductor but a hard metal, chemically very resistant does not rusted. A quality precious metal base Cu, Nb, Ti, it will not bring that quality. With such an expensive electrode, it is not worth the risk poor conductivity, poor quality base. The copper completely erodes in a chlorate perchlorate cell atmosphere. Titanium have poor conductivity. The electrode are tested and working in the long term with the specified parameters.

 

 

Another problem with a small setup, is the limiting factor of an ability to scale up for larger production being prohibitively expensive.

 

I experienced this when I needed (wanted) to produce my own sodium chlorate to feed my perchlorate experiments. I needed a LOT of NaClO₃ to feed my various experiments and for continuity, wanted them all to be fed from the same batch of chlorate crystals; so I built the large scale cell for that purpose.

 

I made a large cell of 12" PVC pipe, with a PVC plate for a base, solvent welded to the pipe (which stands vertically on the base plate). Another piece of PVC plate was fabricated for the lid of the cell, with a silicone tubing seal to prevent salt creep (a pet peeve of mine). This setup provided me a 25 liter cell to facilitate greater sodium chlorate production.

 

On this lid, I drilled and tapped several holes to use PVDF compression fittings and various PVC plumbing fittings for the electrodes, sensors, vent, et cetera; that I use to control and monitor what is happening in the cell as it runs.

 

As per Swede's Blog, I made the leads connected to the larger electrodes (required for the scope of production I planned on) of titanium tubing. The problem was that titanium is so poor a conductor, that I needed to fill it with something much more conductive or the leads would get too hot to be held in polymer fittings.

 

Rather than tin for a filler, as Swede used, I used a solid pure copper rod to fill the titanium tubes, held tightly between the sealed spot-welded end where the electrodes were connected and the brass bolt which held the electrical connections on the other end of the tubes.

 

This worked very well and kept the titanium tubes from getting more than 35^o-45^oC while carrying the higher current required for the larger cell. The system worked well for the entire six week run of the cell. My choice to use pure copper rods in the titanium tubes was economical, because the vastly higher cost of solid silver rods over copper rods wasn't worth it for a mere 3% gain in conductivity. Copper is 97% as conductive as silver but still more than 32 times as conductive as titanium.

 

This works for me because I make up my own electrodes from MMO on CP titanium mesh stock I acquired many years ago, and I tailor them to the power source I use; matching the amperage demand of the electrodes to 80% of the output of the power supply I intend to use.

 

Of course, this is for the chlorate side of things. For perchlorate production, I match the variable output of a good quality power supply to the perchlorate cell's current demand, PLUS I use the power supply in constant current (CC) mode, to simplify my end-of-run calculations. I have (so far) been able to successfully minimize damage to my commercially produced perchlorate anodes by strictly controlling the current feeding them during their runs.

 

As I go forward in my perchlorate experiments (after I can build up a sufficient amount of sodium chlorate crystals for feedstock), I'll see how well the two different perchlorate anodes (Pt and LD) hold up, and then share my finding here in the (per)chlorate thread.

 

WSM

Edited April 24, 2022 by WSM

[WSM]

MMO is the perfect anode for chlorate cells but it will not produce perc. Platinum is the best anode for perc -run carefully to avoid erosion, otherwise lead dioxide is suitable and sometimes ebay can supply.

 

 

This is true, and when I can get back to my perchlorate experiments, I intend to see how well the different available anodes hold up. I would like to document running them to the point of failure (or I get tired of trying), to get a truer picture of which anode is better for the amateur electrochemist to use in small scale perchlorate production.

 

Also, I'd like to document a workable setup for practical (and high quality) perchlorate production on a small scale for amateur pyrotechnists. In a world of uncertain availability of such essential materials, this knowledge will be priceless!

 

WSM

[mx5kevin]

 

 

Another problem with the setup is the limiting the ability to scale up for larger production.

 

I experienced this when I needed (wanted) to produce my own sodium chlorate to feed my perchlorate experiments. I needed a LOT of NaClO₃ to feed my various experiments and for continuity, wanted them all to be fed from the same batch of chlorate crystals; so I built the large scale cell for that purpose.

 

I made a large cell of 12" PVC pipe, with a PVC plate for a base, solvent welded to the pipe (which stands vertically on the base plate). Another piece of PVC plate was fabricated for the lid of the cell, with a silicone tubing seal to prevent salt creep (a pet peeve of mine). This setup provided me a 25 liter cell to facilitate greater sodium chlorate production.

 

On this lid, I drilled and tapped several holes to use PVDF compression fittings and various PVC plumbing fittings for the electrodes, sensors, vent, et cetera; that I use to control and monitor what is happening in the cell as it runs.

 

As per Swede's Blog, I made the leads connected to the larger electrodes (required for the scope of production I planned on) of titanium tubing. The problem was that titanium is so poor a conductor, that I needed to fill it with something much more conductive or the leads would get too hot to be held in polymer fittings. Rather than tin for a filler, as Swede used, I used a solid pure copper rod to fill the titanium tubes, held tightly between the sealed spot-welded end where the electrodes were connected and the brass bolt which held the electrical connections on the other end of the tubes.

 

This worked very well and kept the titanium tubes from getting more than 35^o-45^oC while carrying the higher current required for the larger cell. The system worked well for the entire six week run of the cell. My choice to use pure copper rods in the titanium tubes was economical, because the vastly higher cost of solid silver rods over copper rods wasn't worth it for a mere 3% gain in conductivity. Copper is 97% as conductive as silver but still more than 32 times as conductive as titanium.

 

This works for me because I make up my own electrodes from MMO on CP titanium mesh stock I acquired many years ago, and I tailor them to the power source I use; matching the amperage demand of the electrodes to 80% of the output of the power supply I intend to use.

 

Of course, this is for the chlorate side of things. For perchlorate production, I match the variable output of a good quality power supply to the perchlorate cell's current demand, PLUS I use the power supply in constant current (CC) mode, to simplify my end-of-run calculations. I have been (so far) successfully able to minimize damage to my commercially produced perchlorate anodes by strictly controlling the current feeding the cell during it's run.

 

As I go forward in my perchlorate experiments (after I can build up a sufficient amount of sodium chlorate crystals for feedstock), I'll see how well the two different perchlorate anodes (Pt and LD) hold up, and share my finding here in the (per)chlorate thread.

 

WSM

 

If someone buys platinum don’t have to accept the first offer. Durable thick electrodes can only be small in size at an affordable price for small cells. Ebay is full of fake platinum anodes. Thin pure platinum electrodes without coating like a wire, pure mesh platunum, pure platinum plate are out of the question because their not tolerare 6V 4-6A.

 

Platinum Titan anod: It should only be cleaned by soaking in clean or slightly hydrochloric acid water. If too much volts and amps used the anode will crash fast. In theory, it is much more durable than lead dioxide. 2,5-5micron are very thin. For a 15 liter setup need a large electrode minimum 2″ x 3″ what are ~65$ and very small for a 15l setup, or bigger 1/8" x 1" x 8" would be ideal for a 15 liter cell what are ~130$. A 8 x L. 100mm 2,5 micron Platinum Coated Titanium Round bar ~180$. 150x40 mm 2,5µm Pt 94$. Where not guaranteed minimum 2,5 micron platinum coating it shouldn't be bought either. Rod, Titanium Mesh Coating: Pure Platinum Platinum Thickness: <10um which would be durable. 10 micron this is the thickness of a food grade aluminum foil, 2,5 micron there is an aluminum foil of this size too. 2,5 micron the lower limit below which it should no longer be bought. In a 15 liter cell above 2,5 micron are priceless. Durable electrode above 2,5 micron with a large surface not possible in 10-15l homemade setups. 2,5 microns is so thin that it is ruled out that it will not be ruined over time. If a titanium mesh anode it is important that the stem is also coated with platinum, especially where it is welded.

 

Lead dioxide: They wear out all the time slowly. It can be used to make larger quantities at once like a 15 liter setup.

 

70mm x3 mm x0,2mm (200micron) pure clad platinum in a silver base: From 120$ i buyght the electrode. It costs the same like a larger platinized titanium anode. Guaranteed to last a lifetime but the limit are 6V 6A and 1500ml. Not too much costly in price. Maximum 3 kg KClO4 or KClO3 slowly in a 1500ml cell using several run/1 year are possible comfortably. Making 1 kg KClO4 a basic thing every year.

 

Many people do not write exact parameters how many microns are the coating, how many years it operated, an image of the electrode.

[Arthur]

Platinum electrodes were and maybe still are the go to electrode for the industry.

 

Platinum electrodes do not like supply voltage ripple. Big power supplies used six phase motor generator sets so that ripple was minimised on the rectified DC supply without monster smoothing capacitors. Carefully run cells would erode the platinum at a rate of grams per ton of product. Big platinum sheets were used only a few thou thick the advantage of using thin platinum was that you could use both sides of the platinum not just one side as with plated pt.

Edited April 22, 2022 by Arthur

[kingkama]

KingKama said:

 

"

 

I'd like to give you some advice on how to make your own naclo3. Starting with a saturated solution of nacl, start the electrolysis and add a container full of nacl inside the reaction v Vessel, this will keep the solution saturated at all times. Given the solubility of naclo3 you will often have to add nacl in the prepared container, when the solution is saturated with naclo3 they will begin to form wonderful crystals you just have to fish them out and keep adding nacl.

 

"

 

What temperature do you run the Sodium Chlorate cell at so that you can get solid Sodium Chlorate coming out of solution at the same time that you are getting Sodium Chloride

to go into the solution?

 

Cheers,

 

EB

I don't use a temperature control, this process is simply automatic, when the saturation point is reached the Naclo3 crashes. At the same time Nacl goes into solution Occupying the place released by naclo3 Which has just formed and will saturate the solution, this happens at any temperature, the sodium salts are less sensitive to temperature. Keep in mind that the saturation of Naclo3 per liter is higher than 1 kg, even if this is lowered by the presence of Nacl. Remember the salt out procedure. When a saturated solution of a lighter salt is added to a solution of a heavier salt, the heavier salt precipitates. This is to tell you that if you work with let's say two liters, you add in First 700 grams nacl to have a saturated solution They will produce when fully converted approx 1.5 kilos Of naclo3 that still are few to get a precipitation. You will probably have to add and wait for around 1400 grams of nacl to be processed into Naclo3 to see the first batch sink. At this point the reactor is loaded and will continue to work for as long as you want, as much moles of nacl add as many moles of naclo3 will precipitate. And It is essential that the nacl is added in a perforated container that is immersed in the reactor so that the release is gradual. The pH should be kept on acid by adding HCL and sodium Persulfate.

[mx5kevin]

For a 25l cell platinized titanium anode 150x40 mm (2,5µm Pt) 94$ size will need a minimum. To be held together by two titanium cathodes which is bigger than the anode. The advantage is a faster process and much more tolerate the anode acidic more conditions. 5-7V 40A preferably switch mode power supply required for the process. Need a professional switching power supply which can be precisely controlled in a 25l setup. The run time can be very long up to several months in a NaClO4 cell using more than 10l cell. Running time depends on money and equipment. For a 10-30 l setup professional equipment required. Pro chlorate perch tests. More than 20l precise pH control required where an instrument measures and dispenses this is very costly. This is out of the question for most of us. If someone is experimenting and making KClO4, Ba(ClO3)2, KClO3, HClO4, and not just planning the synthesis of chlorate and perchlorate there need a electrode like the thicker 200 micron pure platinum on a silver base. With 2,5µm Pt can't experiment, stable controlled conditions are required for its use. The setup in WSM Homegrown Oxidizers blog are a professional setup. In a amateur setup the precise costly pH controlling, costly professional switching power supply, precise chlorate tests are not a option it would cost too much. Using an amateur infusion set (like used for plants) with a 5ml/hour regulator for pH control for a 1,5-10l setup much more cheaper. We are are very few of us in this community who will make a pro perchlorate synthesis. Most people who do amateur pyrotechnics a simple flash powder can not make professional on a professional level by by making in product specific.

[kingkama]

For a 25l cell platinized titanium anode 150x40 mm (2,5µm Pt) 94$ size will need a minimum. To be held together by two titanium cathodes which is bigger than the anode. The advantage is a faster process and much more tolerate the anode acidic more conditions. 5-7V 40A preferably switch mode power supply required for the process. Need a professional switching power supply which can be precisely controlled in a 25l setup. The run time can be very long up to several months in a NaClO4 cell using more than 10l cell. Running time depends on money and equipment. For a 10-30 l setup professional equipment required. Pro chlorate perch tests. More than 20l precise pH control required where an instrument measures and dispenses this is very costly. This is out of the question for most of us. If someone is experimenting and making KClO4, Ba(ClO3)2, KClO3, HClO4, and not just planning the synthesis of chlorate and perchlorate there need a electrode like the thicker 200 micron pure platinum on a silver base. With 2,5µm Pt can't experiment, stable controlled conditions are required for its use. The setup in WSM Homegrown Oxidizers blog are a professional setup. In a amateur setup the precise costly pH controlling, costly professional switching power supply, precise chlorate tests are not a option it would cost too much. Using an amateur infusion set (like used for plants) with a 5ml/hour regulator for pH control for a 1,5-10l setup much more cheaper. We are are very few of us in this community who will make a pro perchlorate synthesis. Most people who do amateur pyrotechnics a simple flash powder can not make professional on a professional level by by making in product specific.

This happens because we insist on the use of platinized electrodes, amateurishly the best solution is lead dioxide, indestructible and resistant to all percentages of precursors, using a poor quality platinized electrode as a base, a decent PbO2 electrode can easily be made, Using techniques within the reach of any amateur or bought ready made for half the cost of a platinum electrode on chinese market.

[mx5kevin]

This happens because we insist on the use of platinized electrodes, amateurishly the best solution is lead dioxide, indestructible and resistant to all percentages of precursors, using a poor quality platinized electrode as a base, a decent PbO2 electrode can easily be made, Using techniques within the reach of any amateur or bought ready made for half the cost of a platinum electrode on chinese market.

 

There is no good solution for perchlorate production. Invest with the most durable solution with the fewest tools. PbO2 anode they wear out slowly the process can only be slowed down. The PbO2 are sensitive for too acidic and alkali solution too. PbO2 corrosion in a perchlorate cell are high at the end of the process. Few micron platinum 2,5 micron vulnerable it can't last forever. Thicker platinum small electrodes can be very costly. Then there are the other tools beaker (get cracked). Hotplate get rusted, pH meter it also get ruined. The chlorine gas: the lungs should be protected using a M3 mask with special chlorine filter, safety glass from protect the eyes from chlorine. Safely outdoor can operated the cell (the chlorine gas problem). Lack of routine to use tools which need several years to learn the user to correctly use them. These are the biggest problems. Perchlorates cannot be made cheaply and easily no matter how detailed the instructions. Chlorates are not the solution, they are sources of injury. If someone starts experimenting with homemade anodes, experimenting with alternative solutions (like thermal decomposition) it further multiplies costs and problems significantly. To this comes another big problem that the majority is not even aware of the most basic professional things. A simple pure KClO3 production are problem for the people, see on Youtube there are plenty of videos but no one does it right with a full correct tutorial. Who is experienced (in homemade groups) also does big nonsenses which is refuted by professional documents, literature. The less work, the more efficient, faster, is a very important aspect. It’s worth investing in better tools that make you work less and progress, production are much faster.

Edited April 23, 2022 by mx5kevin

[kingkama]

 

There is no good solution for perchlorate production. Invest with the most durable solution with the fewest tools. PbO2 anode they wear out slowly the process can only be slowed down. The PbO2 are sensitive for too acidic and alkali solution too. PbO2 corrosion in a perchlorate cell are high at the end of the process. Few micron platinum 2,5 micron vulnerable it can't last forever. Thicker platinum small electrodes can be very costly. Then there are the other tools beaker (get cracked). Hotplate get rusted, pH meter it also get ruined. The chlorine gas: the lungs should be protected using a M3 mask with special chlorine filter, safety glass from protect the eyes from chlorine. Safely outdoor can operated the cell (the chlorine gas problem). Lack of routine to use tools which need several years to learn the user to correctly use them. These are the biggest problems. Perchlorates cannot be made cheaply and easily no matter how detailed the instructions. Chlorates are not the solution, they are sources of injury. If someone starts experimenting with homemade anodes, experimenting with alternative solutions (like thermal decomposition) it further multiplies costs and problems significantly. To this comes another big problem that the majority is not even aware of the most basic professional things. A simple pure KClO3 production are problem for the people, see on Youtube there are plenty of videos but no one does it right with a full correct tutorial. Who is experienced (in homemade groups) also does big nonsenses which is refuted by professional documents, literature. The less work, the more efficient, faster, is a very important aspect. Its worth investing in better tools that make you work less and progress, production are much faster.

Well you find the Better way, do nothing, Who do nothing can never go wrong.

[WSM]

For a 25l cell platinized titanium anode 150x40 mm (2,5µm Pt) 94$ size will need a minimum. To be held together by two titanium cathodes which is bigger than the anode. The advantage is a faster process and much more tolerate the anode acidic more conditions. 5-7V 40A preferably switch mode power supply required for the process. Need a professional switching power supply which can be precisely controlled in a 25l setup. The run time can be very long up to several months in a NaClO4 cell using more than 10l cell. Running time depends on money and equipment. For a 10-30 l setup professional equipment required. Pro chlorate perch tests. More than 20l precise pH control required where an instrument measures and dispenses this is very costly. This is out of the question for most of us. If someone is experimenting and making KClO4, Ba(ClO3)2, KClO3, HClO4, and not just planning the synthesis of chlorate and perchlorate there need a electrode like the thicker 200 micron pure platinum on a silver base. With 2,5µm Pt can't experiment, stable controlled conditions are required for its use. The setup in WSM Homegrown Oxidizers blog are a professional setup. In a amateur setup the precise costly pH controlling, costly professional switching power supply, precise chlorate tests are not a option it would cost too much. Using an amateur infusion set (like used for plants) with a 5ml/hour regulator for pH control for a 1,5-10l setup much more cheaper. We are are very few of us in this community who will make a pro perchlorate synthesis. Most people who do amateur pyrotechnics a simple flash powder can not make professional on a professional level by by making in product specific.

 

 

There may be a misunderstanding here.

 

I used the 25 liter cell for making sodium chlorate, not perchlorate. The perchlorate cell needs a LOT of sodium chlorate to make a saturated electrolyte for the process, which is why I scaled up the size of my sodium chlorate cell.

 

My perchlorate cells were typically about 2 to 3 liters, due to my limited access to commercial sodium chlorate (I only had 8 pounds and can't get more). The success of my perchlorate experiments (two cells, one using a platinized titanium mesh anode and the other using lead dioxide on titanium mesh anode), made me curious about making sodium chlorate. I shifted my research to learning how to make enough high purity sodium chlorate, that I could run the rest of my perchlorate experiments from one large collection of sodium chlorate crystals. My research is ongoing...

 

If I were to try such a large scale perchlorate cell, I would want to have 50-100 Kg (110-221 pounds) of sodium chlorate available (NaClO3 is so soluble, a lot goes into making a saturated solution of it).

 

I don't plan to do that because I don't need that much potassium perchlorate. My experiments are mostly "proof of concept" experiments, plus teaching myself how it can be done safely, on a small scale. I also want to share the results of my research for others to learn from, much the same as Swede did while he wrote here (see his blog posts).

 

WSM

Edited May 1, 2022 by WSM

[WSM]

For a 25l cell platinized titanium anode 150x40 mm (2,5µm Pt) 94$ size will need a minimum. To be held together by two titanium cathodes which is bigger than the anode. The advantage is a faster process and much more tolerate the anode acidic more conditions. 5-7V 40A preferably switch mode power supply required for the process. Need a professional switching power supply which can be precisely controlled in a 25l setup. The run time can be very long up to several months in a NaClO4 cell using more than 10l cell. Running time depends on money and equipment. For a 10-30 l setup professional equipment required. Pro chlorate perch tests. More than 20l precise pH control required where an instrument measures and dispenses this is very costly. This is out of the question for most of us. If someone is experimenting and making KClO4, Ba(ClO3)2, KClO3, HClO4, and not just planning the synthesis of chlorate and perchlorate there need a electrode like the thicker 200 micron pure platinum on a silver base. With 2,5µm Pt can't experiment, stable controlled conditions are required for its use. The setup in WSM Homegrown Oxidizers blog are a professional setup. In a amateur setup the precise costly pH controlling, costly professional switching power supply, precise chlorate tests are not a option it would cost too much. Using an amateur infusion set (like used for plants) with a 5ml/hour regulator for pH control for a 1,5-10l setup much more cheaper. We are are very few of us in this community who will make a pro perchlorate synthesis. Most people who do amateur pyrotechnics a simple flash powder can not make professional on a professional level by by making in product specific.

 

 

I humbly submit that my setup isn't "professional", but perhaps it may more accurately be described as an advanced amateur setup.

 

I have found that scaling up a setup, requires much more control and monitoring. Through careful eBay searches and researching the subject over a long period of time, I have slowly begun to acquire many hard-to-find and otherwise expensive pieces of equipment to help me make progress in my experiments.

 

Well over a decade ago, my first successful potassium chlorate cell was a one-gallon glass pickle jar with a 4" PVC pipe cap for a lid. It made a good amount of raw KClO₃ crystals from electrolyte of dissolved KCl water softening salt, before I began to further improve my setups.

 

I continue to learn as I go. Never stop learning; it's helping this old man to keep a youthful attitude !

 

WSM

[markx]

There is no good solution for perchlorate production. Invest with the most durable solution with the fewest tools. PbO2 anode they wear out slowly the process can only be slowed down. The PbO2 are sensitive for too acidic and alkali solution too. PbO2 corrosion in a perchlorate cell are high at the end of the process. Few micron platinum 2,5 micron vulnerable it can't last forever. Thicker platinum small electrodes can be very costly. Then there are the other tools beaker (get cracked). Hotplate get rusted, pH meter it also get ruined. The chlorine gas: the lungs should be protected using a M3 mask with special chlorine filter, safety glass from protect the eyes from chlorine. Safely outdoor can operated the cell (the chlorine gas problem). Lack of routine to use tools which need several years to learn the user to correctly use them. These are the biggest problems. Perchlorates cannot be made cheaply and easily no matter how detailed the instructions. Chlorates are not the solution, they are sources of injury. If someone starts experimenting with homemade anodes, experimenting with alternative solutions (like thermal decomposition) it further multiplies costs and problems significantly. To this comes another big problem that the majority is not even aware of the most basic professional things. A simple pure KClO3 production are problem for the people, see on Youtube there are plenty of videos but no one does it right with a full correct tutorial. Who is experienced (in homemade groups) also does big nonsenses which is refuted by professional documents, literature. The less work, the more efficient, faster, is a very important aspect. It’s worth investing in better tools that make you work less and progress, production are much faster.

 

Ah bollox....don't be so apocalyptic! This is supposed to be an enjoyable and educational activity. Most of the appeal lies in the process of learning how to do it properly....if one's only goal is to summon oxidizing agents cheaply, then amateur electrosynthesis is not the path to turn to. And it surely will rob a fair amount of years to learn it. Even if one has an educational background that suits the purpose.

I do agree with the notion that a whole lot of people do not have the faintest clue of what they are doing and are unable to assess the sensibility (or rather the lack of) of their activities. This definitely amounts to a lot of failure and financial loss.

But I do not agree that an amateur approach with a fair amount of defiance towards "undisputed facts stemming from professional literature" is unable to achieve success. Obviously a failure is imminent if one starts bashing around in a senseless way, but taking the scientific/technological information with a grain of salt while keeping a cool analytical mindset is often the key to improving things even in a very simple setting.

As far as perchlorate electrosynthesis goes there are a lot of claims that make life interesting: E.g. "one needs a cell voltage upwards of 5V to make perchlorate on Pt", "chlorides are a big no-no when Pt is used", "one needs meticulously purified chlorate solution for the perch cell" , "KClO4 does not form electrochemically from a KClO3 solution on Pt", "it is detrimental to start perchlorate electrosynthesis directly from chloride with Pt anode" etc. For my practical purposes I've proven for myself that all of the abovementioned claims are either wrong or have a very marginal significance in an amateur setting:

Perchlorate forms very nicely on Pt with a cell voltage as low as 4,2V.....chloride contaminated electrolyte vs purified chlorate solution yields about the same amp hours before Pt coated Ti passivates......chloride forms as a byproduct from chlorate in perchlorate synthesis stage......KClO4 forms directly on Pt (coated) anode in a KClO3 solution and flakes off (very impressive to watch btw)....and I routinely go from sodium chloride solution into full perch conversion in a single run with Pt coated Ti.

There are two significant factors when it comes to perchlorate electrosynthesis:

1) the anode is expendable (unless a solid brick of Pt is at hand) , accept it and find a source for replacement...or learn to coat Ti with Pt like I did.

2) Keep the cell voltage as low as you can to make the anode less expendable during a longer term of service.

Everything else is pretty much petty cash.

 

Thermally deposited Pt coating on CP Ti that serves as an expendable anode:

 

Edited April 24, 2022 by markx

[mx5kevin]

Recommended NaClO3 concentration for NaClO4 production by professional literature.

 

http://www.chlorates.exrockets.com/encyperc.html

 

https://www.iasj.net/iasj/download/b657a529c35af648

 

For making NaClO4 semi-concentrated NaClO3 used (Sodium chlorate 400 gpl). From concentrated NaCl to NaClO3 wil get this solution semi-concentrated. I don't usually add it more NaCl, I only control pH. From chlorate specific to perchlorate specific changed the anode before NaClO4 started to forming (tested with a methyline blue) and sugar with NaClO3. And the NaClO3 concentration was high this point changed the anode to perchlorate specific anode. Nothing other was done with the cell solution. Most of the literature does not write concentrated NaClO3 they a semi-concentrated solution is recommended. And this semi-concentrated solution will get automatic way from concentrated NaCl solution without user interaction. The solution will become increasingly unsaturated as the process progresses. It is possible to add more NaCl to the NaClO3 solution. I have read that this is detrimental to the electrode and slows down the process if very concentrated the NaClO3 solution (Not the NaCl). But the NaClO4 weight from NaCl are from every 100g NaCl will be 210g NaClO4. And when the NaClO4 are high and minimal NaClO3 left behind extreme erosion effect get the anode. Nor is there a requirement to wait until the last minute wehen NaClO4 start forming, can replace the electrode before this point. That would be the problem if MMO anode will used to chlorate perchlorate production. And when the methyline blue test show positive perchlorate test this point not changed the MMO anode to PbO2 or Pt. This would harm the electrode. Perchlorate formation will not begin until chlorate formation is complete. What I experienced not recommended to reuse the NaCl solution after the KCl+NaClO4 reaction, its full of perchlorate. Much less chlorine is released from the system the MMO electrode, on the other hand, is subject to multiple erosion. Feeding exra NaCl when reused the solution it would make more sense. This, in turn, is not good for a MMO or a thicker platinum anode.

[eb666]

I don't use a temperature control, this process is simply automatic,

 

 

when the saturation point is reached the Naclo3 crashes. At the same time Nacl goes into solution Occupying the place released by naclo3 Which has just formed and will saturate the solution, this happens at any temperature, the sodium salts are less sensitive to temperature. Keep in mind that the saturation of Naclo3 per liter is higher than 1 kg, even if this is lowered by the presence of Nacl. Remember the salt out procedure. When a saturated solution of a lighter salt is added to a solution of a heavier salt, the heavier salt precipitates. This is to tell you that if you work with let's say two liters, you add in First 700 grams nacl to have a saturated solution They will produce when fully converted approx 1.5 kilos Of naclo3 that still are few to get a precipitation. You will probably have to add and wait for around 1400 grams of nacl to be processed into Naclo3 to see the first batch sink. At this point the reactor is loaded and will continue to work for as long as you want, as much moles of nacl add as many moles of naclo3 will precipitate. And It is essential that the nacl is added in a perforated container that is immersed in the reactor so that the release is gradual. The pH should be kept on acid by adding HCL and sodium Persulfate.

What temperature does the cell run at? (I would like to know).

 

I tried running a chlorate cell at 70C and at 50C . The anode was the usual type of MMO .

The cell was started with a saturated solution of sodium chloride.

Each cell had a container of solid NaCl (sodium chloride) and the NaCl was exposed to the cell liquid with lots of stirring.

The NaCl had lots of surface area exposed to the solution.

The sodium chlorate concentration kept going up and up but the NaCl concentration kept dropping untill it was too low for

proper operation of the anode. The concentration of the NaCl was starting to go below 50 grams per litre with no Chlorate coming out of solution

at 50C (or at 70C).

In my opinion the cell temperature must be somewhere (I don't know exactly where) below 50C for a continous operation to be achieved.

The situation will be worse if you increase the running temperature because the Chloride (NaCl) solubility will not change much and the

Na Chlorate will be very much less inclined to come out of solution.

 

When I stopped the cell, and the temprature fell, lots and lots of Chlorate came out of solution and coated EVERYTHING in the cell, bottom, sides, anode, cathode, stirrer.......

 

What I am trying to say is this.

You cannot run a sodium chlorate cell at 50C (or above) continously and harvest chlorate from the cell and keep adding solid

NaCl to replenish the harvested chlorate.

It did not work for me. The chloride level in the liquid goes too low for proper operation of the cell (anode).

Perhaps it will work if you allow for some evaporation from the cell. There was no evaporation from my cell.

I don't consider stopping the cell, to let the temperature fall, continous operation and anyways when you do that

you get sodium chlorate ALL OVER THE PLACE where it is diffucult to harvest/scoop out.

 

Evaporation can be difficult to implement without the 'dreaded mist' problem. This is a mist coming from the cell which rusts all in the surroundings!

 

 

I have done something similar with a perchlorate cell. Keep adding sodium chlorate solution (I did not try adding a bag or container of solid sodium chlorate)

and you will see sodium perchlorate starting to appear on the bottom of the cell where you can scoop it out.

The sodium chlorate will keep at a sensible concentration (for anode operation) because it is sufficiently soluble even at high

perchlorate concentrations (where the perchlorate will start to ppt out of solution).

There may have been some evaporation of water out of this perchlorate cell.

 

EB

Edited April 27, 2022 by eb666

[kingkama]

What temperature does the cell run at? (I would like to know).

 

I tried running a chlorate cell at 70C and at 50C . The anode was the usual type of MMO .

The cell was started with a saturated solution of sodium chloride.

Each cell had a container of solid NaCl (sodium chloride) and the NaCl was exposed to the cell liquid with lots of stirring.

The NaCl had lots of surface area exposed to the solution.

The sodium chlorate concentration kept going up and up but the NaCl concentration kept dropping untill it was too low for

proper operation of the anode. The concentration of the NaCl was starting to go below 50 grams per litre with no Chlorate coming out of solution

at 50C (or at 70C).

In my opinion the cell temperature must be somewhere (I don't know exactly where) below 50C for a continous operation to be achieved.

The situation will be worse if you increase the running temperature because the Chloride (NaCl) solubility will not change much and the

Na Chlorate will be very much less inclined to come out of solution.

 

When I stopped the cell, and the temprature fell, lots and lots of Chlorate came out of solution and coated EVERYTHING in the cell, bottom, sides, anode, cathode, stirrer.......

 

What I am trying to say is this.

You cannot run a sodium chlorate cell at 50C (or above) continously and harvest chlorate from the cell and keep adding solid

NaCl to replenish the harvested chlorate.

It did not work for me. The chloride level in the liquid goes too low for proper operation of the cell (anode).

Perhaps it will work if you allow for some evaporation from the cell. There was no evaporation from my cell.

I don't consider stopping the cell, to let the temperature fall, continous operation and anyways when you do that

you get sodium chlorate ALL OVER THE PLACE where it is diffucult to harvest/scoop out.

 

Evaporation can be difficult to implement without the 'dreaded mist' problem. This is a mist coming from the cell which rusts all in the surroundings!

 

 

I have done something similar with a perchlorate cell. Keep adding sodium chlorate solution (I did not try adding a bag or container of solid sodium chlorate)

and you will see sodium perchlorate starting to appear on the bottom of the cell where you can scoop it out.

The sodium chlorate will keep at a sensible concentration (for anode operation) because it is sufficiently soluble even at high

perchlorate concentrations (where the perchlorate will start to ppt out of solution).

There may have been some evaporation of water out of this perchlorate cell.

 

EB

You are rigth the cell I was telling you about is open and the temperature is quite low, use 18 amps with one anode and two cathodes mmo / ti. To reduce the corrosive fog I added a plexiglass cover that also holds the electrodes in place. The precipitation probably occurred due to a cooling of the cell,From which the precipitated Naclo3 was not removed. In the previous post I said an inaccuracy that is that the temperature does not affect the solubility of naclo3, this is wrong. I believe the cell temperature rarely exceeds 50 degrees and I suspect that it is often even lower, because, the maximum electrolysis power is never used, the range is from 15 to 18 amps. I suspect that you have not yet reached the maximum saturation point relative to the operating temperature of your cell, According to the solubility table at 60 Degrees Celsius the solubility is 1,300 kg liter so you will easily find yourself having several kilos dissolved. The starting weight of the NACL is about one third of the naclo3 So with a small two-liter cell you will begin to see something when at least one and a half kilograms of Nacl are dissolved. I have stumbled upon this method by chance, since operate the cell in the best possible saturation conditions, With the lower voltage and consequently the lower temperature. Adding sodium persulfate in the ratio of 2 grams per liter and up to 8 grams per liter helps to avoid cathodic decomposition This also increases efficiency and therefore waiting time.

How do you check the saturation of the naclo3 and the Nacl, I don't do it to the maximum I add a little water to keep the level constant, I have no mixing system because I think it is useless, as a container for the nacl I have a plastic bottle perforated all over the surface, Which is completely immersed in the cell.

Edited April 27, 2022 by kingkama

[eb666]

Hello,

 

You need a mixing system if the anode and cathode do not go all the way to the bottom of the cell. You will get a dead zone on the bottom as the bubbles from the cathode will not

mix the bottom few inches.

 

I think the cells I ran at 50C and 70C were saturated with both Na chlorate and chloride because when I took a small sample from the cell and cooled it, a small amount, I got a ppt of stuff (pure chlorate I presume).

I monitored Na Chloride concentration by titration.

The cells where pH controlled.

 

The graph from EKA Chemicals is not accurate for a cell AFAICS.

It may be accurate for a professionally operated crystallizer where there are less dissolved gasses (guessing) and perhaps some circulating seed crystals of sodium chlorate that help the chlorate to come out of solution (another guess). Comments welcome.

Temperatues in a crystallizer can also be varies as opposed to a one bucket cell which stays at a fairly steady temperature.

The EKA graph is here www.chlorates.exrockets.com/akagraph.html first graph.

Link does not work. Type it in if you want.

 

 

I think that if you want to have a sodium chlorate cell that is run continously AND get the full advantage of pH controll (run the cell hot) then you are going to simply have to use

a two container system. One bucket for the electrodes (hot) and a cooler crystallizer (another bucket!!).

You don't get full advantage of pH controll if you run the cell at say 40C or below. But there is nothing wrong with that. It is more work and trouble making and running the more complicated system.

Another reasons for needing the second chamber (cooler) is that sodium chlorate is inclined to ppt out like concrete. It gets everywhere you don't want it and it is difficult to remove. You cannot simply scoop it out of the cell. It will also ppt out on top (and cover) the sodium chloride that you are trying to expose to the electrolyte and this will stop it from dissolving into the liquid electrolyte. It's not like potassium chlorate that comes out of solution as fluffy crystals on the bottom of the cell and can be scooped out.

 

EB

Edited April 27, 2022 by eb666

[kingkama]

To EB666

I have noticed that chlorate tends to form wonderful crystalline structures that are hard to Break but only when left to crystallize in tranquility, otherwise it becomes like coarse sand. I had also thought about using a two stage cell, but I preferred to use a simpler system, with minimal pH control and using persulfate to reduce cathodic reduction.

Probably having turned the reactor off and on And having worked in a very cold environment I managed to have a massive and sudden precipitation. It could also be that the dead zone may have acted as a concentrator, since this zone will have received the heavier Naclo3 salts and the higher part the lower Nacl concentration which would explain because the consumption of Nacl remains constant (if it is consumed it is because it passes into solution)

Edited April 27, 2022 by kingkama

[mx5kevin]

For a high yield effective fast NaClO3 cell which produces quickly especially for large quantities buying a chlorinator electrode are the best. This was using multiple large surface area close to each other MMO anode and titanium cathode. Which is use 3 MMO and 4 titanium cathode it is also much more effective than a single MMO titanium combination. The process time can be reduced to half or a quarter by the electrodes. Or it can be multiplied the runtime if the surface is small and the solution are too much. PC 5V 15A and used server power supplies 5V 17A for larger cells 5-10l , 6V 4-6A car battery charger for 0,5-5l setup are cheap. But it should not be overheated with it the cell. A cooler setup much more ideal than a hot setup. Using with this 6V and precisely controlled amps so as not to overheat the cell with pH control the most effective solution. If possible, keep the electrodes as deep as possible in the solution. Without regularly pH control the process are much more slower, less effective. It can be used effectively extra amps and the alkali acidic reaction are fast. The process works in winter outdoor too for chlorate production the hot cell it's not necessary. When the cell heated to 90°C at the beginning and added HCl to get more acidic sulution than pH 6. It can't even produce chlorate, after hours when the pH goes alkali and HCl are added no reaction occurred. And it should have happened with chlorate. The system only produced chlorine, chlorate could not be formed and in acidic condition due to strong heating the chlorate was decomposing. And the other problems hot cells reduces electrode life. Have to make a concentrated NaCl solution at the beginning and keeping the pH 6-7 close to pH 7 neutral until the end of the process. If the cell is warm and not too hot 40-45°C for a homemade chlorate cell are ideall. Above 50°C in homemade setups negative effects begin to occur. If to the cell few drops HCl are added at the beginning of the process and there was no reaction there is a problem. I have tried several times to increase the temperature to speed up the process. In any case, this causes more problems than it has benefited. The real solution is to use large surface area electrodes close to each other. And the MMO anode with 2 titanium cathode be inserted between so that the chlorine formed at the anode is neutralized as quickly as possible. The external temperature is constantly changing in the room. In summer are 30° and winter are -10°C. 60-80°C in a factory setup where the solution is circulated, precise pH control are used they can be cooled at the electrodes, everything is feasible what in homemade setups are not. I've seen it from several people to running homemade chlorate cells at 50-60°C. I failed to drastically speed up the process by heating. I have experienced several disadvantages to heating as an advantage.

[mx5kevin]

Electrodes and the cell too have a limit how much amps are tolerate. If need to cool externally that are problem. The platinum electrode can be destroyed with it very easily this way. As a rule of thumb no more than 2 amperes per 100 ml of electrolyte must be passed through a chlorate cell (Preparing chlorates PyroGudie). This is a very high value compared to the tolerance of the electrodes. If chlorate and perchlorate are maked which is a advanced pyro hobbyist make not just making chlorate. Need to be calculated to use the same setup to chlorates and perchlorates too. For perchlorate production the temperature must kept under 45°C or the electrode life will be short. Without external cooling must keep the cell this temperature. If it's too hot the user most use less amps to protect the anode. There is a lower limit and an upper limit how much chlorate/perchlorate can product the same setup. Subsequent development and modification costs a lot.

 

Surface and size of electrodes the and the used Amps the most important thing that determines the speed of production. If not enough Amps are used or the surface of the electrodes is small the process will be very slow or not working. When used minimum 4A the process is sure to work but more than 1,5l possible will be slow. If the electrodes are not have large surface enough than extra amps make trouble. If the cell overheats it is also a problem. The process cannot be significantly accelerated with extra amps if the electrodes surface are not enough large. The cell will be heated and the electrodes will be destroyed in this case. Must avoid to overheat the cell this will only cause problems. It is much better to spend more time on the process in a cooler cell max 50°C for making chlorate.

 

I did a calculation I will update if I find something wrong with it:

 

https://www.amateurpyro.com/forums/blog/45/entry-171-the-homemade-chlorate-and-perchlorate-project/

 

For 1,5l-5l (or 10l maximum) computer or used server power supply with 5V 15-17A with connecting together parallel thin wires ideal to cheap way set the required amps for the cell without costly adjustable precision PSU (with adjustable current Amps). This must be measured and calculated accurately for the current cell how much amps. For 0,5-1,5l cell 6V 4-6 A using a car battery charger are perfect. In small cells it's harder to make mistakes. The problem are above more than 1,5l cells. A lot of people overload the electrodes, ond overheat the cell and this and turns out after several uses.

 

Using a 50x200mm, 60x150mm MMO and PbO2 anode at this size max 15A which they tolerate without a problem. (Factory data is the exact data provided by a seller). Wit the same size MMO and PbO2 can be calculated the same amps. If the chlorate cell runs 30-50°C only the anode needs to be replaced. There will be no problem the setup are too hot for a perchlorate cell, or using too much amps for the anode. There will also be no problem with the life of the cell setup by reducting it the too much heat.

 

Platinized Titanium Mesh Anode 1" x 4" or 2" x 3" 2,5 micron 6V 6A maximum which they tolerate without a problem in long term. (I inferred this on my own setup and other users setups like in the sciencemadness forum).

 

A salt water swimming pool chlorinator using 10 and 30 Amps 6-9V what using multiple MMO and Titanium cathode, and several liters of water pass through it. A homemade setup using maximum 1 anode and 2 cathode. There is a big difference based on usage but a good calculation basis.

 

In specification the factory show the current mA/Cm2 Platinum, MMO, and PbO2 too which says nothing to most amateurs.

 

Chlorinator:

 

https://easierwithpractice.com/how-many-amps-does-a-salt-chlorinator-use/

 

https://poolmasta.nz/salt-chlorinator-information/

 

My opinion 0,5l-1,5l setup using a 6V 4-6A car battery charger for on average 1-2kg KClO3, KClO4/year are enough if someone is not planning to expand the setup (have a fix volts, amps, temperature without calculation for chlorate, perchlorate production too). And with this setup with plus Ba(ClO3)2, NH4ClO4 can also be made conveniently with the 1-2kg KClO3 and KClO4. MMO and PbO2 combination, MMO and few micron platinum, or a thicker platinum clad anode by self all good for this setup. If something goes wrong, the costs will less. It is much cheaper to solve with fewer devices. Such is the digital pH meter if the electrode tolerate highly acidic and alkali conditions it can also be set up with cheap tools how much HCl will need to use.

Edited April 30, 2022 by mx5kevin

[mx5kevin]

Mixing and filtering NaClO4, KClO3 concentrated hot solutions to get KClO4 are much more ideal than mixing NaClO4 with KCl. The are no wastewater so the process are cheaper, does not have chloride contamination in the perchlorate cell and perchlorate contamination in the chlorate cell what are both have a huge chlorate and perchlorate anode erosion potential. A lot of NaCl, HCl and production time is saved which significantly reduces costs. Which seriously damages these electrodes. And the production are much more faster. KClO3 can be prepared much more faster than NaClO3. And converting NaClO3 to NaClO4 are much more faster than converting NaCl->NaClO3->NaClO4 in every time. However, there are also disadvantages the potassium must be carefully extracted by concentrating and cooling the solution so that it does not precipitate on the anode. Destroying the chlorates, and recrystallization all must be done with the KClO4. Here, experience is required for someone to do it well. The most effective and cheapest method for potassium perchlorate production that I have found so far. See patent CN102807192A Potassium perchlorate production technology with zero wastewater discharge and products thereof. The best way to convert KClO3 to KClO4 with eletrolysis are using NaClO4 for the process.

[PillaDoubleG]

Maybe this was mentioned in this thread, but what thickness titanium should I use for a perc cell???
I know that people say the thickness should be above 1mm, so I was wondering if I could possibly get away with 1.5mm?
For context, I will be using a PbO2 anode, and the titanium plate is 100x100x2 or 100x100x1.5.

 

[WSM]

On 4/22/2022 at 3:40 AM, mx5kevin said:

It is very important to use the right tools for the purpose. ...

... Digital pH meter: Need to calibrate with pH buffers, and always wash it with NaHCO3 solution after used in the chlorate, perchlorate cell ...

Might I suggest washing and storing the pH sensor in KCl solution immediately after testing, instead of using bicarbonate. The potassium chloride solution will help prevent permanent damage to the sensor internals, and help maintain them for MUCH longer than if no protection is used. Chlorate tends to poison the sensor, especially inexpensive ones. 

The chlor-alkali industry uses very expensive pH sensors which resist poisoning... to a point. Unless you're prepared to spend up to $1000 for a high-end pH sensor and detection system, please treat you pH testers better. 

As an alternative, DI water wetted pH paper can give a clue as to the pH just before it is bleached by the electrolyte. Quick observation of the moist end of the dipped pH paper should approximately indicate the pH of the chlorate solution sample, as a thin band, before the bleaching occurs. Thanks to Mumbles for this suggestion.

WSM

[taiwanluthiers]

I got some questions about the power supply used in a cell.

I'm wanting to try this again, but I remember (years ago) I tried using a computer power supply and when using platinum or lead dioxide anode, they were failing almost immediately, because the computer power supply is constant voltage, and it simply can't supply more than 1 amp in a perchlorate cell unless the electrode is nearly touching, even for a half gallon cell.

So I got this idea: What about using a DC stick welder? It's basically a constant current supply, the voltage varies to maintain a current. They have a duty cycle but that's if you're running them at max amp (which is usually around 250 amps for a 220v welder). We'll be running at the low end, 20 amps max, it can run for weeks this way.

I can get lead dioxide anode from Taobao. They also have MMO and the titanium cathode and even supply cell containers.

Is there any reason not to use a stick welder running on DC? We're talking about inverter stick welders, not that Lincoln tombstone stuff that's AC.