making potassium (per) chlorate

[Arthur]

There is certainly a good repertoire of chlorate formulae, colours, effects and noise.

[taiwanluthiers]

We just need better instruction as far as chlorate formulas. Problem is most literature (Shimzhu, Lancaster, etc.) have too little information on chlorate since it was regarded as dangerous. Older formula is hard to find since everyone keeps them a secret.

[lloyd]

Part of the problem with any British author's contribution to the chlorate discussion is that chlorates been illegal there since the late 1800s.

 

But today's modern PURE potassium chlorate, along with purer fuels (like acid-free sulfur) have improved the safety margin.

 

If you wish to read about chlorates, pursue literature by Italian or Maltese authors, or writings by Mike Swisher or A. Fulcanelli in Pyrotechnica editions IX and XI.

 

SOME chlorate compositions have been (more recently) used by a few US manufacturers of special effects, but they must be tested by a professional 'certification' laboratory for sensitivity and stability before they will be approved -- and that's HARD to get and expensive. Amateurs use them all the time to great effect for both color and burn time.

 

Lloyd

[Arthur]

Not quite! The first British Explosives Act and all the subsequent ones prohibit compounds where chlorate is mixed with either sulphur or phosphorus without special licence. Some compounds simply NEED chlorates, just that they cannot in the UK also contain sulphur or phosphorus. However the need for a completely separate production place for chlorate comps does introduce severe limitations.

 

Bit i still wouldn't want to mill chlorates in a mill that also did BP, no matter how "safer than before" it may be.

[lloyd]

Thanks for clarifying that. I think the reading references might be of some use.

 

LLoyd

[taiwanluthiers]

I think chlorate and sulfur mixes have been used as corrosive rifle primers...

[memo]

i sure would like to get it to where i am making perchlorate instead of chloate. still a little uneasy useing chlorate. i know it has a lot of uses, flash bags and bottom shots still give me the willies.

 

memo

[OldMarine]

Mike Swisher uses chlorates almost exclusively in his color stars and that's a smart dude.

[Arthur]

Using chlorates in the right way is no problem, in fact the original colours in pyro were largely chlorate comps. However some comps that used calomel (mercury compound) Paris Green (arsenic compound) and sometimes lead nitrate do now have extra hazards understood.

 

Chlorates act as chlorine donors and hence help most colours,

 

The two issues are getting a good formulary with lots of colours and effects while being careful of the incompatabilities, and sorting out a selection of lifts, breaks and primes to minimise the internal friction between incompatable components.

 

Whether or not they were due to impurities there have been some terrible incidents with chlorate comps, in particular several deaths when a toy gun cap factory exploded (chlorate and red P ) and hundreds of deaths when someone tried commercial bulk BP production using chlorate subbed for nitrate.

[WSM]

i sure would like to get it to where i am making perchlorate instead of chloate. still a little uneasy useing chlorate. i know it has a lot of uses, flash bags and bottom shots still give me the willies.

memo

 

If perchlorates are your goal and you're making sodium chlorate, you're already halfway there. See if you can isolate the sodium chlorate crystals. Then if you can dissolve and recrystallize the sodium chlorate, I think it'll be pure enough for a perchlorate cell.

 

Make a solution of sodium chlorate with pure water (minimum 600 g per liter, up to 750 g per liter) and run it in a new cell with your platinum anode and titanium cathodes (if you can get CP titanium sheet metal). I recommend feeding the cell 4-5.5 Vdc and 0.2 A per cm² and I think you'll succeed (I did).

 

If you do this and it works the way my cell did, you'll notice an ozone smell coming from the vent (right away) and before many hours you can detect perchlorate in the electrolyte with the methylene blue solution in a spot test.

 

When run to completion, the next step is to destroy the residual chlorate (I used sodium metabisulfite solution, testing for chlorate between doses). When the sodium perchlorate solution is chlorate-free, convert it to potassium chlorate by metathesis with potassium chloride solution, wash the KClO4 crystals with pure water and vacuum filter to remove the liquids. I usually follow the separation with pure water rinses while the vacuum is still running, which helps remove traces of the soluble sodium contaminants. after all this, dry and store the purified potassium perchlorate.

 

It sounds like a lot of work, but a good final product is worth the effort.

 

WSM

[WSM]

Whether or not they were due to impurities there have been some terrible incidents with chlorate comps, in particular several deaths when a toy gun cap factory exploded (chlorate and red P ) and hundreds of deaths when someone tried commercial bulk BP production using chlorate subbed for nitrate.

 

Yes, but remember this was almost 200 years ago.

 

This lesson was learned early on and the warnings went out far and wide. The warning is still valid today. We can use chlorate safely, if we understand its nature and respect it. Never take any shortcuts with safety and always wear proper PPE's (Personal Protective Equipment) while you work with high energy materials. We tend to forget (in our excitement and enthusiasm) the potential hazards of our activities, and we must not allow ourselves to become complacent.

 

WSM

[taiwanluthiers]

I did that with potassium chlorate, I got ozone but then the cell current dropped off to nothing and the platinum stripped off completely. No idea what was at play there. There was also no detectable trace of perchlorate at all.

[TomasBrod]

I did that with potassium chlorate, I got ozone but then the cell current dropped off to nothing and the platinum stripped off completely. No idea what was at play there. There was also no detectable trace of perchlorate at all.

 

It is impossible to make perchlorate from potassium chlorate due to is's low solubility.

[Mumbles]

Impossible, no. Impractical, probably.

[schroedinger]

It is impossible to make perchlorate from potassium chlorate due to is's low solubility.

Not at all. Swede demonstrated it, and documented it very god in his the bucket cell blog. They key factor for this is temperature control, you need to keep the temperature above 50ºC to have enough chlorate dissolved in the liquor.

[taiwanluthiers]

That was what I did actually. I used external heat source to keep the temperature up, but I had trouble keeping current up. Swede's blog states that potassium perchlorate (which is insoluble) formed almost immediately, but no such thing happened even at optimal condition, just lots of ozone. In the end it became impractical... at least ever since coming to America, at least until they make that stupid explosive precursor law some day (and I hope the NRA prevents that by extension)

[WSM]

Not at all. Swede demonstrated it, and documented it very god in his the bucket cell (?) blog. They key factor for this is temperature control, you need to keep the temperature above 50ºC to have enough chlorate dissolved in the liquor.

 

In Swede's blogs (you'll put your eye out), check the 6 September 2008 blog. It's well written and has usable information. If I had the ability to contact Swede, I'd ask him further details, such as the voltage and current settings of his power supply and whether he used CC mode or not, plus the temperature of the electrolyte as it ran. Also I don't recall if that run was platinum on titanium (platinized titanium) or lead dioxide on titanium.

 

WSM

[OldMarine]

Try sending Swede a PM. He's still listed as a member.

[WSM]

Try sending Swede a PM. He's still listed as a member.

I just checked; the last time he was active here was nearly three and a half years ago.

 

Too bad, it would be good to talk with him again.

 

WSM

[taiwanluthiers]

I believe he used platinized titanium at one run and his own LD at another. Both gave the same result but of course platinized titanium would wear out faster.

[WSM]

1) I believe he used platinized titanium at one run and his own LD at another.

2) Both gave the same result but of course platinized titanium would wear out faster.

 

1) You're right, if my recollection is correct.

 

2) This is also correct, from what I've seen.

 

As for making potassium perchlorate from potassium chlorate using a platinum anode, the best scenario was suggested as using a smooth, solid anode, so the crystals might more easily fall out rather than collect in the openings of a mesh anode.

 

I don't know if this is real or just wishful thing, since the potassium perchlorate drops out of solution as it's formed (even at fairly high temperatures and relatively high velocities).

 

Industry avoids the direct conversion of potassium chlorate to perchlorate, not because it's "impossible", but because of the horrible inefficiency of the process. Despite the attraction of avoiding sodium contamination of the final product (which sounds attractive to us, the users of that product), industry uses the sodium chlorate to sodium perchlorate to potassium perchlorate method; finding it preferable to keep sodium contamination out by rigorous purification methods between process steps (and possibly also after the potassium perchlorate is formed), as the most cost effective method of production.

 

After making my own potassium perchlorate by metathesis of purified sodium perchlorate (made by electrolyzing sodium chlorate solution in both Pt and PbO₂ cells), I agree with industry as to which system is best to produce potassium perchlorate. If fact, I'm leaning toward LD as the better anode to use between the two. If I have a chance to use other perchlorate anodes in the future, my preference might change; but since those are the only two I have available and have experience with, this is my current opinion.

 

WSM

Edited June 27, 2016 by WSM

[WSM]

Try sending Swede a PM. He's still listed as a member.

 

I recall posting PM's in the past, to no avail. If he reads them, he chooses not to respond.

 

I suspect his interests have taken him elsewhere.

 

WSM

[WSM]

That was what I did actually. I used external heat source to keep the temperature up, but I had trouble keeping current up. Swede's blog states that potassium perchlorate (which is insoluble) formed almost immediately, but no such thing happened even at optimal condition, just lots of ozone. In the end it became impractical... at least ever since coming to America, at least until they make that stupid explosive precursor law some day (and I hope the NRA prevents that by extension)

 

Without knowing a host of the particulars of your setup, it's not possible to give any suggestions as to why your attempt failed and the anode disintegrated. We can only guess, and unless we have more information, that's as far as it can go.

 

If you ever decide to try again, mention it here and we can suggest things to note or observe before you start to build, so you might have the best chance of succeeding; or at least learn the reason for a failure with the best conditions to learn from it, overcome the obstacles and achieve ultimate success.

 

The present conditions here in the US allow us to purchase the materials we use in our hobbies. If that changes, these discussions might change from theory to necessity, if we want to continue entertaining with fireworks. I hope that doesn't happen but time will tell...

 

WSM

Edited June 26, 2016 by WSM

[taiwanluthiers]

If we can't get perchlorate at all in the US then something terrible has happened to get there, and we will have bigger things to worry about. I'd say if the second amendment somehow gets repealed or completely ignored, and gun availbility is on the level of UK, then we would probably have to worry about pyro material availbility too.

[WSM]

If we can't get perchlorate at all in the US then something terrible has happened to get there, and we will have bigger things to worry about. I'd say if the second amendment somehow gets repealed or completely ignored, and gun availbility is on the level of UK, then we would probably have to worry about pyro material availbility too.

 

 

Okay, but that's not the case here and now.

 

If those sorts of things happen, we deal with them (and you're right, if we start seeing that sort of shenanigans in and by the government, we'll have bigger issues than where we'll get our fireworks for entertainment).

 

WSM

Edited June 26, 2016 by WSM