making potassium (per) chlorate

[50AE]

We successfuly welded MMO to CP Ti with a tungsten welding system! Sadly, I don't have photos, but I will soon, because I ordered all my MMOs to be welded.

[pyrojig]

We successfuly welded MMO to CP Ti with a tungsten welding system! Sadly, I don't have photos, but I will soon, because I ordered all my MMOs to be welded.

 

Sweet!!!!!

How expensive was the wire to weld it with?

[Bonny]

I remember patsroom saying if there are chips in the LD, to keep those parts out of the liquid. I imagine the concern is not letting the liquid cause separation between the LD and the titanium substrate (which would be witnessed by lowering current levels as the damage progressed). He said that was the only help the manufacturer of the LD would offer. We have to try the anodes and see.

 

I wonder if running sodium chlorate would work any better than potassium chlorate?

 

WSM

 

There were no visible chips that I saw, but there could have been. The current is still the same as when I started. I AM approaching the end of my calculated run time though, so I will be shutting down probably today or maybe tomorrow. Then I can have a good look at the anode.

 

What if perchlorate was forming inside the surface on the LD anode? crystals forming on it might have roots or something that did into the soft anode and as they grow they chip off lead dioxide, like tree roots in pavement. im fairly certain that in swedes blog there is an image of perchlorate forming on the anode, but i think he was using sodium in his cell.

 

Interesting idea and I guess the crystals could form and break off the LD...

 

IIRC Swede did not do any experiments with sodium. I have never had perc forming on the anode, with the current LD or with the Pt anodes I used before.

[oldmanbeefjerky]

well there's that theory down the drain..........

however, there always is the chance that your electrodes arent as good as swede. and maybe unable to handle that current. try it again at 10 amps, and see if it shows any sings of corrosion.

poorly plated lead dioxide is 1/10th as porous as compressed graphite, and lead dioxide electrodes should never be porous.

its my understanding though that lead dioxide doesnt like potassium hydroxide, and swedes cell was kept as a mostly neutral acidity if im not mistaken

[Bonny]

well there's that theory down the drain..........

however, there always is the chance that your electrodes arent as good as swede. and maybe unable to handle that current. try it again at 10 amps, and see if it shows any sings of corrosion.

poorly plated lead dioxide is 1/10th as porous as compressed graphite, and lead dioxide electrodes should never be porous.

its my understanding though that lead dioxide doesnt like potassium hydroxide, and swedes cell was kept as a mostly neutral acidity if im not mistaken

 

 

I am running my cell at 10A. Most of the details were posted here recently... The LD anode is one purchased from another member here. Based on the size (4x6 or something) it should safely handle a lot more current than that.

After this run, when I get around to it, I'll try again as maybe all the crap that is going to come off already has...

[WSM]

After this run, when I get around to it, I'll try again as maybe all the crap that is going to come off already has...

 

Hopefully you're right and the dark mess stops. The last time I saw dark stuff in a cell, it was a cell jar of polyethylene which didn't like the alkaline environment of the active (non-pH controlled) cell. The PE plastic was breaking down and plenty of black crud was getting in the KClO₃ crystals. That's when I switched to the glass pickle jars.

 

I have a friend who runs his cell in a polyethylene container and has no problems, but he controls the pH to about 6.5-7 (he also gets over 90% efficiency).

 

WSM

[oldmanbeefjerky]

well if you havent already take this up with that member. these anodes shouldnt do that, at least not that fast .

[hillbillyreefer]

I think I'm ready to build and test out my cell. Here is what I plan to do. 20L bucket, screw on airtight lid, breather tube vented to the outdoors, salvaged power supply 5v 20 amp, laserred mmo anode, 316 stainless cathode, start out with a saturated kcl solution to keep it simple. The anode and cathodes are about 3"x12".

 

Thanks to all the trailblazers for posting their methods. While the chlorate is being made I need to reread this thread for the third time to pick up a few more pointers on the perc side of things.

[oldmanbeefjerky]

i really need some container that is clear like glass, but wont ruin my anodes.

first though, since i dont yet have my MMO, ill use an ipod, instead, because it is such a high grade steel.

 

ill only convert 100g anyway

 

 

all i need to do is add enough hot water to completely dissolve the chlorate that precipitates out, filter out the iron oxide, then boil down to slightly less volume until it precipitates, and all is good!

or section off the ipod with nylon wool(from synthetic pillow) or fiberglass. these wont be destroyed by the cell will they?which would mean i just need to scoop out the precipitated chlorate

Edited July 27, 2011 by oldmanbeefjerky

[WSM]

i really need some container that is clear like glass, but wont ruin my anodes.

first though, since i dont yet have my MMO, ill use an ipod, instead, because it is such a high grade steel.

ill only convert 100g anyway

all i need to do is add enough hot water to completely dissolve the chlorate that precipitates out, filter out the iron oxide, then boil down to slightly less volume until it precipitates, and all is good!

or section off the ipod with nylon wool(from synthetic pillow) or fiberglass. these wont be destroyed by the cell will they?which would mean i just need to scoop out the precipitated chlorate

 

You can test the plastic or other materials by sticking them in a container of bleach (sodium hypochlorite) for a week or two. Of course that's only half the picture; there's no current going through the bleach to perfectly simulate the cell environment.

 

Nylon is not compatible if I remember correctly. The fiberglass depends on what form it is and what grade of glass (I don't know the details).

 

PVC plastic is perfectly compatible and good below a maximum temperature of 60^oC (in fact, I'd keep it below 50^oC). Other materials are also compatible but much more expensive or harder to find. They do make clear PVC pipe and fittings but they are really expensive unless you get lucky and find a cheap source like a scrap yard or recycler who has some.

 

A google search of materials compatibility for the material you are considering using and the chemicals expected in the testing environment would be useful. Happy hunting...

 

WSM

Edited July 27, 2011 by WSM

[WSM]

I think I'm ready to build and test out my cell. Here is what I plan to do. 20L bucket, screw on airtight lid, breather tube vented to the outdoors, salvaged power supply 5v 20 amp, laserred mmo anode, 316 stainless cathode, start out with a saturated kcl solution to keep it simple. The anode and cathodes are about 3"x12".

Thanks to all the trailblazers for posting their methods. While the chlorate is being made I need to reread this thread for the third time to pick up a few more pointers on the perc side of things.

 

The anode size you're using can handle more that three times the current you're putting through it (if properly connected), so everything should work fine, and that anode will last a very long time if not abused some other way. I think the stainless cathode will last longer if you keep the pH lower (between 6.5 and 7). If you decide to upgrade to CP titanium, the cathode will also last a very long time and the product will be very pure (no extra ions floating around with it).

 

Wait, you said cathodes, then change that to more than six times the current you're using. It should work fine for very long time if I'm correct.

 

Let us know how it goes...

 

WSM

[Bonny]

Hopefully you're right and the dark mess stops. The last time I saw dark stuff in a cell, it was a cell jar of polyethylene which didn't like the alkaline environment of the active (non-pH controlled) cell. The PE plastic was breaking down and plenty of black crud was getting in the KClO₃ crystals. That's when I switched to the glass pickle jars.

 

I have a friend who runs his cell in a polyethylene container and has no problems, but he controls the pH to about 6.5-7 (he also gets over 90% efficiency).

 

(WSM

 

Rememeber I am running a perc cell atm.

 

Was the PE he was using black? My buckets are white. Standard white colour additive for PE us TiO2, but I doubt that is causing anything.

 

i really need some container that is clear like glass, but wont ruin my anodes.

 

I used HDPE buckets for 5 or more runs of chlorate, with no ph control. I have never had any colour issues (black crap) until I started running perc. I am convinced that LDPE will NOT damage a good quality MMO anode. Mine still looks like new after months of running.

[pyrojig]

I have to ask ......,

What was the CE% that you got w/o PH control? How do that environment ( no ph control) wear on the MMO anode and the TI cathode?

 

 

Rememeber I am running a perc cell atm.

 

Was the PE he was using black? My buckets are white. Standard white colour additive for PE us TiO2, but I doubt that is causing anything.

 

 

 

I used HDPE buckets for 5 or more runs of chlorate, with no ph control. I have never had any colour issues (black crap) until I started running perc. I am convinced that LDPE will NOT damage a good quality MMO anode. Mine still looks like new after months of running.

[Bonny]

I have to ask ......,

What was the CE% that you got w/o PH control? How do that environment ( no ph control) wear on the MMO anode and the TI cathode?

 

I was never really concerned with cell efficiency, but calculated once at 50-60% IIRC (it was a few years ago).

 

The anode will be fine if you simply run until the current (amps) drop. My cell ran about 20-25A, I would stop when it dropped to ~15A.

I have no visual wear on the anode after several runs (5 or 6). The Ti cathode should last indefinitely.

[WSM]

I have to ask ......,

What was the CE% that you got w/o PH control? How do that environment ( no ph control) wear on the MMO anode and the TI cathode?

 

The CE% w/o pH control is less than 60%. MMO and Ti are unaffected in either system. With MMO and titanium electrodes and less than maximum power run through them, they should last many years of constant use (and I don't know anyone running theirs constantly).

 

Of course, with pH control CE% is commonly over 90%.

 

WSM

[oldmanbeefjerky]

A Pool filter (fiberglass , for removing insoluble calcium from water before it enters the pool) should hold up right?

I'm only going to be using it though in cells for testing out how well alternative anodes work, like lead ,steel and iPod touch's.

 

The CE% w/o pH control is less than 60%. MMO and Ti are unaffected in either system. With MMO and titanium electrodes and less than maximum power run through them, they should last many years of constant use (and I don't know anyone running theirs constantly).

 

Of course, with pH control CE% is commonly over 90%.

 

WSM

 

 

one must always be careful not to get the cells acidity beyond neutral, or complications like the formation of chloric acid(HClO3), begin to occur, which i can imagine wouldn't be that good for the electrodes or the cell's walls, regardless of what the compound is.

 

I'll try again as maybe all the crap that is going to come off already has...

 

Ive done some digging, and im sad to tell you that your anode may have been improperly produced!

If a lead dioxide anode is made at a current density of over 50ma/cm2, then the anode will be most likely be 50/50 alpha and beta, if it is at the recommended amount which is under 20ma/cm2, then it will often be only ~1-5% alpha, but all the alpha which can be accessed from the surface will often come off the surface, and then the entire surface will only consist of beta. and any more will be probably locked down by the beta.

Anyway, my point is that if done improperly, the anode will erode like yours is.

 

this leads me to beleive that maybe all hope is not lost for the lead acetate idea, and i will once again start making lead and copper acetate to build a lead dioxide electrode, though when i plate it, i think ill need to keep the current extremely low, like 2ma/cm2.

the person who first told me about the idea of making a lead dioxide electrode, didnt specify which compound he uses, only that he plates it at 2ma/cm2, which is well below whats required for nitrate plating, and this is done on a rotating carbon substrate.

 

i would go and ask whoever made your LD electrode, what current they made it with.

Edited July 28, 2011 by oldmanbeefjerky

[WSM]

Rememeber I am running a perc cell atm.

 

Was the PE he was using black? My buckets are white. Standard white colour additive for PE us TiO2, but I doubt that is causing anything.

 

I used HDPE buckets for 5 or more runs of chlorate, with no ph control. I have never had any colour issues (black crap) until I started running perc. I am convinced that LDPE will NOT damage a good quality MMO anode. Mine still looks like new after months of running.

 

We're possibly talking apples and oranges here. The PE in the uncontrolled chlorate cell was affected where with pH control there was no noticable affect (the PE was clear or white, by the way).

 

With a perchlorate cell we're not dealing with hypochlorites but primarily breaking water and forcing oxygen onto chlorate. Hydrogen is discarded and some telltale ozone is liberated if I understand it right.

 

WSM

[WSM]

A Pool filter (fiberglass , for removing insoluble calcium from water before it enters the pool) should hold up right?

I'm only going to be using it though in cells for testing out how well alternative anodes work, like lead ,steel and iPod touch's.

one must always be careful not to get the cells acidity beyond neutral, or complications like the formation of chloric acid(HClO3), begin to occur, which i can imagine wouldn't be that good for the electrodes or the cell's walls, regardless of what the compound is.

 

I don't know enough to judge whether the pool filter will hold up or not. You may have to try it and see.

 

The running (chlorate) cell naturally goes alkaline as it runs. Neutral (pH 7.0) gets it close but just misses the mark. Running the cell slightly acidic is the optimal condition for highest efficiency. The goal is a pH of 6.5 to 6.8, but anywhere close has proven effective.

 

By all means avoid getting close to a pH of 6.0 or below where free chlorine starts to evolve and creates a health risk. If you read Swede's blog, he mentions creating a diffuser tube for the hourly dilute acid injections, so the acid slowly and evenly enters the cell; not shocking it and releasing chlorine gas (as just dumping it onto the surface of the liquid tends to do). In his system, Swede injects a measured amount of dilute acid based on the current draw of the system and the progress of the batch.

 

Any chloric acid formed in solution is reacted with MOH (M=either sodium or potassium) and is never in the free state where it would be a problem.

 

WSM

[Bonny]

Ive done some digging, and im sad to tell you that your anode may have been improperly produced!

If a lead dioxide anode is made at a current density of over 50ma/cm2, then the anode will be most likely be 50/50 alpha and beta, if it is at the recommended amount which is under 20ma/cm2, then it will often be only ~1-5% alpha, but all the alpha which can be accessed from the surface will often come off the surface, and then the entire surface will only consist of beta. and any more will be probably locked down by the beta.

Anyway, my point is that if done improperly, the anode will erode like yours is.

 

this leads me to beleive that maybe all hope is not lost for the lead acetate idea, and i will once again start making lead and copper acetate to build a lead dioxide electrode, though when i plate it, i think ill need to keep the current extremely low, like 2ma/cm2.

the person who first told me about the idea of making a lead dioxide electrode, didnt specify which compound he uses, only that he plates it at 2ma/cm2, which is well below whats required for nitrate plating, and this is done on a rotating carbon substrate.

 

i would go and ask whoever made your LD electrode, what current they made it with.

 

That could very well be. The cell is shut down. There are a few pcs of LD coating that broke off and the surface is much smoother looking than when I started.

I'll still try another run and see if it will still produce perc. I want to use up all my raw chlorate if I can, and I think I have enough for 1 more bucket cell run.

 

I think the anode was made in either China or India, so getting answers is unlikely.

Hopefully once you make a good working LD anode, you'll have some available for sale

 

We're possibly talking apples and oranges here. The PE in the uncontrolled chlorate cell was affected where with pH control there was no noticable affect (the PE was clear or white, by the way).

 

With a perchlorate cell we're not dealing with hypochlorites but primarily breaking water and forcing oxygen onto chlorate. Hydrogen is discarded and some telltale ozone is liberated if I understand it right.

 

WSM

 

I have never used ph control and have not had any discoloration in chlorate runs using a PE bucket, maybe there was something else in his cell???

 

Perc cell definately produce ozone!!

My first perc run a couple years did not have outside venting and the ozone smell was horrible. I had to shut the cell down and get a vent tube hooked up.

[pyrojig]

The CE% w/o pH control is less than 60%. MMO and Ti are unaffected in either system. With MMO and titanium electrodes and less than maximum power run through them, they should last many years of constant use (and I don't know anyone running theirs constantly).

 

Of course, with pH control CE% is commonly over 90%.

 

WSM

 

Yes you are correct...

I prefer the ph control as well. Im doing it "caveman style" , I have a injection syringe in the cell that I correct the ph with. Here is where it gets weird, and may be something to do with the venting tubes of the cell. ( which are 2x 3/16" poly tubes= 3/8 "total venting ) . I'm not sure if it is enough venting.... the cell (5gal hdpe bucket) runs very warm + 50* C. Im not sure if it creates some kind of catalytic reaction of sorts, and doesnt let too much gas escape, keeping the ph easier to control !!! I dont need much acid at all. I use 1/4 of what Swedes using per same size cell volume. If I used a timed release sys (or dosed by amp hours) then the cell would be very acidic. This is very strange to me... SO , I dose acid as needed, taking samples of the cell PH in the morning and evening .

 

I realized something else ..... of interest using ph papers. Due to the high salt concentration it seems to "poison" the paper not giving a accurate reading. I water down the sample from the cell with about 50% water, and test it then. I will get a good tester at some point... If I'm not mistaking, the kind that can stay in the cell during operation are very expensive ! I may need to use a cheaper hand held and test it daily I guess....

[oldmanbeefjerky]

That could very well be. The cell is shut down. There are a few pcs of LD coating that broke off and the surface is much smoother looking than when I started.

I'll still try another run and see if it will still produce perc. I want to use up all my raw chlorate if I can, and I think I have enough for 1 more bucket cell run.

 

I think the anode was made in either China or India, so getting answers is unlikely.

Hopefully once you make a good working LD anode, you'll have some available for sale

 

 

 

I have never used ph control and have not had any discoloration in chlorate runs using a PE bucket, maybe there was something else in his cell???

 

Perc cell definately produce ozone!!

My first perc run a couple years did not have outside venting and the ozone smell was horrible. I had to shut the cell down and get a vent tube hooked up.

 

 

it could still be a while,

however silly me, discovered that the northern territory based public lab chemical inventory sells nitric acid AR grade 70%, for $29/500ml and $63/2.5L, right after i prepared my crude lead nitrate setup!

. though its my understanding that once i get some nitric acid (to make lead and copper nitrate), so long as i keep my cell free from impurities, i can almost continuously plate lead dioxide without the need for expensive new acid to make more nitrate, so long as i keep introducing new copper and lead into the cell between and during batches to keep the acid levels low and "recharge" the cell with new lead nitrate and copper nitrate, and also so long as i keep the cell running at a very low voltage and very low current density, to avoid "free flowing nitrate ions" , which apparently wont form nitric acid.

 

 

If i do manage to make lead dioxide anodes which work, i will obviously have some available for sale, because if they work the way their meant to, i wont really need more than 1 or 2 as they will last be ages.

 

I wonder if that ozone could be utilized in some way? perhaps , it might be able to form hydrogen peroxide, in a (very strong) UV chamber and reintroduced into the perchlorate cell to raise the cell efficiency!

its just a thought.....probably wont work.

but it could be used to make red iron oxide and other metal oxides quickly, which is always useful

Edited July 29, 2011 by oldmanbeefjerky

[WSM]

That could very well be. The cell is shut down. There are a few pcs of LD coating that broke off and the surface is much smoother looking than when I started.

I'll still try another run and see if it will still produce perc. I want to use up all my raw chlorate if I can, and I think I have enough for 1 more bucket cell run.

I think the anode was made in either China or India, so getting answers is unlikely. Hopefully once you make a good working LD anode, you'll have some available for sale

I have never used ph control and have not had any discoloration in chlorate runs using a PE bucket, maybe there was something else in his cell???

Perc cell definately produce ozone!!

My first perc run a couple years did not have outside venting and the ozone smell was horrible. I had to shut the cell down and get a vent tube hooked up.

 

Hi Bonny,

 

Hopefully the anode is only altered and not ruined.

 

China is the source (I asked).

 

I'll sign up for one once they are proven .

 

It is possible something else was there or some additive in the polymer.

 

Venting away from the workspace and people is always a good idea .

 

WSM

[WSM]

Yes you are correct...

I prefer the ph control as well. Im doing it "caveman style" , I have a injection syringe in the cell that I correct the ph with. Here is where it gets weird, and may be something to do with the venting tubes of the cell. ( which are 2x 3/16" poly tubes= 3/8 "total venting ) . I'm not sure if it is enough venting.... the cell (5gal hdpe bucket) runs very warm + 50* C. Im not sure if it creates some kind of catalytic reaction of sorts, and doesnt let too much gas escape, keeping the ph easier to control !!! I dont need much acid at all. I use 1/4 of what Swedes using per same size cell volume. If I used a timed release sys (or dosed by amp hours) then the cell would be very acidic. This is very strange to me... SO , I dose acid as needed, taking samples of the cell PH in the morning and evening .

I realized something else ..... of interest using ph papers. Due to the high salt concentration it seems to "poison" the paper not giving a accurate reading. I water down the sample from the cell with about 50% water, and test it then. I will get a good tester at some point... If I'm not mistaking, the kind that can stay in the cell during operation are very expensive ! I may need to use a cheaper hand held and test it daily I guess....

 

Hi pyrojig,

 

For a 20 liter cell, I'd recommend larger vents (3/16" tube has about 25% the volume of 3/8" tube; volume vs linear length ). I have a friend who runs his cell very warm, too; and he says the same thing (not as much need for acid injections as cooler cells). Why this is, I don't know yet. There must be a factor we're overlooking.

 

Putting in too much acid is definately a bad idea as free chlorine coming out is the usual result .

 

Diluting the solution sounds like a good idea when doing pH measurements. pH pens (electronic) are as susceptible to poisoning from the cell liquor as the more expensive units. It's usually best to quickly rinse the sensor with running water immediately after getting the read to prolong the life of the unit as long as possible. Sooner or later the sensor will be poisoned; later is better .

 

WSM

[oldmanbeefjerky]

erm, your saying the warm cell isnt loosing chlorine as quickly?

maybe this be due to the heat catalyzed reaction of Cl + XOH → XClO +H

 

generally chemicals are less reactive when cooler. and the bonding of hydroxide and chlorine to make chlorite is something which works more efficiently at elevated temperatures.

[Mumbles]

erm, your saying the warm cell isnt loosing chlorine as quickly?

maybe this be due to the heat catalyzed reaction of Cl + XOH → XClO +H

 

generally chemicals are less reactive when cooler. and the bonding of hydroxide and chlorine to make chlorite is something which works more efficiently at elevated temperatures.

 

 

That post makes me want to stab my computer screen for all the terrible terrible chemistry you've just spewed fourth.