making potassium (per) chlorate

[WSM]

Thanks for the fast responding.

My liquor runs at about 80 degrees celcius at daytime and don't know about the night time. But i'll have to invest in a ampmeter, that can take so high current (36 amp), as my current meters fuse would burn over at 20 amps.

,

When i extracted the yield from the liquor, i cooled it down in a icebath, so it was roughly 5 dregrees, and then filtered the liquor twice as i saw there was formed new crystals in the filtered liquor.

 

Also the build of my cell, the distance between the anode and the cathode, are 15 mm, is this correct or could i improve here? My liquor container is a closed system with a tube in the lid, running down into some water. Will this water filter out some of the chlorine gas or have i been miss informed?

 

Renaxi

Hi renaxi,

 

That seems very warm. The last time I ran a cell it ran about 55 degrees C, all the time. To measure temperature, either a non-contact IR sensor or a digital panel meter with a teflon coated sensor can be found on eBay. Also on eBay, a DC digital ammeter panel meter with a shunt can be had for $12 or less from China.

 

I don't chill my electrolyte to recover the chlorate for fear of dropping out chloride also. I just take what drops out at room temperature and recharge the electrolyte with chloride and run it again.

 

Your electrode gap is fine. I've run a gap from over 100mm down to 3mm and they all work (but with varying efficiency).

 

To react any free chlorine, the best suggestion I've heard was run the vent gasses through a dry hydroxide bed and convert it to harmless salt.

 

WSM

Edited March 8, 2014 by WSM

[pyrojig]

I second the suggestion of not dropping the temp to a cold state. I recharge the liqueur while still fairly on the warm side . As WSM said, You dont want chlorides to drop out of solution too. The warm to moderately hot solution will be almost 100% kclo3 in crystal form. A wash from distilled refrigerated water while filtering , will rid the remaining chlorides that may cling to the crystals . In recent study by Swede , he claims almost 100% chloride free kclo3 from by doing this method. In past I was doing the extra step to recrystallize the batch for ultimate purity .But, This is unnecessary for 99% of pyro-related comps.

[Arthur]

If you want maximum output per batch then cool the electrolyte and get all the chlorate out, but with risk of added chloride being co-precipitated.

 

Cleaner chlorate comes if you only precipitate some of it and keep the rest in solution to pull out later after the next runs.

[WSM]

The concern about chloride contamination in chlorates is that chlorides tend to sensitize chlorates.

 

For greater stability, remove any chlorides from your chlorate.

WSM

Edited March 11, 2014 by WSM

[DasKapital]

Can anybody confirm if ruthenium and iridium oxide mmo anodes can make perchlorate? I have read a lot of patents and literature and some of them say perchlorates while others stop short and only say they produce chlorates.

[WSM]

Can anybody confirm if ruthenium and iridium oxide mmo anodes can make perchlorate? I have read a lot of patents and literature and some of them say perchlorates while others stop short and only say they produce chlorates.

 

Someone here used laserred MMO (which is reportedly ruthenium/iridium MMO) and mentions trying to make perchlorate with it and could only make chlorate. I recall a study of a technical article regarding making and using MMO referring to the "oxygen potential" of various components. Platinum and lead dioxide as well as a few other materials, have the proper oxygen potential to convert chlorate to perchlorate. MMO is designed to be used in the chlor/alkali industry.

 

I suppose these comments will give more questions than answers, but I think I'm on the right track.

 

WSM

[DasKapital]

I wonder if that person tried on k chlorate as well as Na chlorate? From the testing I've done it seems to make a difference. My setup only uses the potassium chlorate salt and I have only been successful with Pt anodes. I've tried with commercial lead dioxide with no results and also with home made. That's why I was wondering about the ruthenium iridium oxide mix. From what I last read, it's oxygen producing overpotential is quite low, and if I've understood correctly, this is undesirable as it makes oxygen easier instead of what we want? Edited March 13, 2014 by DasKapital

[mabuse00]

 

The concern about chloride contamination in chlorates is that chlorides tend to sensitize chlorates.

WSM - or anybody else - could you explain that?

Some kind of catalysis?

 

Is that a proven phenomenon? Do you have any references?

Or just an assumption?

 

 

And imagine there is metal around, magnalium in a water bound star would be likely.

What will corrode the magnalium more - the chlorate or the chloride? (Could that be the dangerous effect?)

 

I'd like to know that in general, I'm not a chemist and never found time to understand the mechanisms properly, but is there some way to calculate that? NaCl vs. NaClO3 and KCl vs. KClO3?

 

The table on shimizu FAST p. 126 states that NaCl is much more corrosive than KClO3, but does not include KCl.

[Mumbles]

I might have been the one to bring the chloride sensitization up initially. I'll take a look and see what I have saved, and see what I can find from legitimate references. Basically the issue is that chloride will reduce chlorate to a minor extent down to chlorite (ClO2 -) and hypochlorite (ClO -). Even present in trace amounts, these compounds will increase the sensitivity to impact and other forms of initiation.

 

You can see some mention of the ability of chloride to reduce chlorate here: http://en.wikipedia.org/wiki/Chlorite

 

The chlorides of both salts are likely much more corrosive to metals that the related chlorates. Then again, I'd not very likely to ever make much in the way of metallic chlorate fueled stars.

[WSM]

WSM - or anybody else - could you explain that?

Some kind of catalysis?

Is that a proven phenomenon? Do you have any references?

Or just an assumption?

And imagine there is metal around, magnalium in a water bound star would be likely.

What will corrode the magnalium more - the chlorate or the chloride? (Could that be the dangerous effect?)

I'd like to know that in general, I'm not a chemist and never found time to understand the mechanisms properly, but is there some way to calculate that? NaCl vs. NaClO3 and KCl vs. KClO3?

The table on shimizu FAST p. 126 states that NaCl is much more corrosive than KClO3, but does not include KCl.

 

Magnalium is a wildcard. It's not a true alloy but an intermetallic mixture. The component metals (aluminum and magnesium) break down in both acid (Mg) and alkali (Al) environments. I don't have specific data about salt reactions but suspect neutral salts ought to be okay (but research or test them on a case by case basis for safety).

 

I'll let Mumbles answer the chloride question.

 

WSM

[WSM]

I might have been the one to bring the chloride sensitization up initially. I'll take a look and see what I have saved, and see what I can find from legitimate references. Basically the issue is that chloride will reduce chlorate to a minor extent down to chlorite (ClO2 -) and hypochlorite (ClO -). Even present in trace amounts, these compounds will increase the sensitivity to impact and other forms of initiation.

 

You can see some mention of the ability of chloride to reduce chlorate here: http://en.wikipedia.org/wiki/Chlorite

 

The chlorides of both salts are likely much more corrosive to metals that the related chlorates. Then again, I'd not very likely to ever make much in the way of metallic chlorate fueled stars.

 

Hi Mumbles,

 

If you can give a definitive answer on this question, we'll all be benefitted by it. Thanks for taking this on (and for the chloride/chlorate warning so long ago).

 

It goes to show how important cleaning and purifying our products is. Thanks again.

 

WSM

[pyrojig]

http://www.oxidizing.110mb.com/chlorate/safety.html

 

Here is a link

 

But with this said, there is very little substantial info out there to prove what " sensitivities" are created by the kcl contamination . It could be another "wise tale" or opinion for that matter . I would only guess that it may have the possibility of lowering the ignition temp , but in mining they used salts to lower the heat of the gases produced ( in coal mining , etc) . .................So, I really am not sure other than what was mentioned earlier , that the chlorides may be a prob for metal containing comps , or others that react with chlorides .

Edited March 14, 2014 by pyrojig

[WSM]

http://www.oxidizing.110mb.com/chlorate/safety.html

 

Here is a link

 

But with this said, there is very little substantial info out there to prove what " sensitivities" are created by the kcl contamination . It could be another "wise tale" or opinion for that matter . I would only guess that it may have the possibility of lowering the ignition temp , but in mining they used salts to lower the heat of the gases produced ( in coal mining , etc) . .................So, I really am not sure other than what was mentioned earlier , that the chlorides may be a prob for metal containing comps , or others that react with chlorides .

 

Hi pyrojig,

 

Thanks for sharing this link. I've been reading through it and many points about chlorate safety are made (I'm particularly benefitting from the chlorate/sulfur section), but precious little is mentioned directly about chloride sensitization of chlorates (or chlorate compositions) except as a reference to some other writing or a vague warning (maybe I need to reread it more carefully!).

 

I wish there were more; this may be an important safety point. If anyone finds something definitive, please share it here.

 

WSM

Edited March 25, 2014 by WSM

[pyrojig]

Well as always there are conflicting views and agendas with chlorates .

I was reading through the "Pyrotechnics " by Hardt on pg 8 2nd paragraph from the bottom. It claims that the use of Sodium chloride to Phlegmatize( desensitize) sodium chlorate( or chlorate in general) from the use in street explosives or illegal fireworks in Europe . The Sodium chlorate was being extracted from "weed killer" . I guess the prob may lie in the fact the chlorides may react with the metal fuels ( aka flash) being the reason it is claimed to be dangerous......... but i am only speculating ....

[schroedinger]

Yes, in europe you could get 70% NaClO3 30% NaCl as a weed killer for a long time. Before this, you could buy 100%.

The reason was that it had been very popular to mix thee 100% stuff with sugar to build B mbs by kids. But still anybody who news a little about chemistry knows that adding KCl would result in pure KClO3

[WSM]

Yes, in europe you could get 70% NaClO3 30% NaCl as a weed killer for a long time. Before this, you could buy 100%. The reason was that it had been very popular to mix thee 100% stuff with sugar to build B mbs by kids. But still anybody who news a little about chemistry knows that adding KCl would result in pure KClO3

 

It sounds like you could jump start a sodium chlorate cell using this mixed salt by adding sodium hypochlorite and sodium chloride to it in solution. After it's converted to NaClO₃ either exchange with KCl to KClO₃ and NaCl or use it as feed stock for a perchlorate cell. Given the proper setup and supplies, I see no problem ,

 

WSM

Edited April 17, 2014 by WSM

[Arthur]

Sadly the EU banned chlorate herbicides a few years ago.

[pex]

Hello,

 

I have a question. I sold a pbo2 anode from a chinese supplier. But with shipping. There are a few bits broken, the anode is 100×100 mm.you can see the titanium. I want to make perchlorate. From pure naclo3. Do any one now of the damage is a big deal.

 

Thanks

 

Pex

[schroedinger]

Normally it shoulndn't be a problem.

 

Arthur Sodium chlorate is still available in the EU, but not as a weed killer, now it gets sold for cleaning stone plates

[pex]

There are a few suppliers in europe. A few paint stores in Belgium Sell it for leathe r. Treatment. This stuf is almost pure. 99.9%

[WSM]

Hello,

I have a question. I sold a pbo2 anode from a chinese supplier. But with shipping. There are a few bits broken, the anode is 100×100 mm.you can see the titanium. I want to make perchlorate. From pure naclo3. Do any one now of the damage is a big deal.

Thanks

Pex

 

Hi Pex,

 

A few years ago I bought two similar sounding PbO₂ anodes. They both came with the same damage as you describe, deep chips on the LD coating. I have hesitated to use them for fear of causing further damage (the coating coming off or a separation between the LD and the titanium substrate.

 

I've considered patching them with some type of polymer but haven't gotten around to trying it yet. Another thought was to set up an LD plating bath and add a bit more beta-form LD to the anodes in hopes of filling in the damaged areas. I also want to spot weld and fill tubular titanium leads to the straps so I can seal the leads in PVDF compression fittings in the lid of the cell (read through Swede's Blogs).

 

In short, I have them but haven't tried using them yet. I don't know if they'll work or if they do, will they be compromised because of the chipped coating. If no one else tries one with similar damage, I may have to venture and see what happens. We'll see...

 

WSM

Edited April 18, 2014 by WSM

[WSM]

I've submitted Part 4 of the series, Homegrown Oxidizers, for publication in the PGI Bulletin. If you're a PGI member, let me know what you think. Sadly, I still haven't received the last issue of the Bulletin (with Part 3 in it) yet, but hopefully soon.

 

I still plan to do a blog here someday, based in those articles.

 

WSM

[taiwanluthiers]

So where do I get this lead dioxide anode from this chinese supplier? Why hasn't anyone tried using them and see how it works? I mean worst it can happen is that it comes apart... I mean I have used MMO anodes with a bit of titanium exposed and nothing seems to happen. If you're reluctant to try it I'd like to get some and try it, and see what happens.

Edited April 18, 2014 by taiwanluthiers

[WSM]

So where do I get this lead dioxide anode from this chinese supplier? Why hasn't anyone tried using them and see how it works? I mean worst it can happen is that it comes apart... I mean I have used MMO anodes with a bit of titanium exposed and nothing seems to happen. If you're reluctant to try it I'd like to get some and try it, and see what happens.

A year or more ago, patsroom was selling them for about $55US. I bought one and later a second one. I don't know whether they were chipped before they left China, during the way to patsroom, at patsroom's place or on the way to my place. All I know is that they both arrived with damage.

 

This is a common theme, I'm afraid. I don't know of anyone who tried to use the anode yet. Maybe we're all waiting for someone else to risk theirs first!

 

Maybe I'll just have to step up and try one and report back here.

 

WSM

[Arthur]

One simple theory is that the Chinese produce LOTS of perchlorate so their anodes may work, The trouble is that the Chinese will sell you anything and call it anything, so you need to try it to be sure.