making potassium (per) chlorate

[WSM]

I've found a little time to work with titanium metal in an effort to make a cathode cage for a friend's bucket cell. The sticking point has been solid blocks to be used as pillars between the 0.050" CP titanium sheet metal used for the cathode plates.

 

I've cut some from some 0.500" CP titanium plate a friend gave me, that are about 0.375" wide (my spacing goal) and 0.200' thick. When all the parts are spot welded together, the spacing between the anode and cathodes will be between a tenth and an eighth of an inch.

 

I'll try to photo-document the process and post it here.

 

WSM

[taiwanluthiers]

Not me, nor have I heard of it; but if you tried it and it proved to work, I don't think I'd be overly surprized.

 

Platinum group metals have interesting properties; their use as catalysts is not the least among them. If you have access to some Pd and try it, let us know what you discover !

 

WSM

 

I don't really have a lot of money at the moment, and while Pd is cheaper (in fact much cheaper, like about 1/5th the price to be exact) it's still fairly expensive and not sold in gram bullions like Platinum. It's about 500 to 600 dollars an ounce at the moment, which compared to platinum is cheap. I guess I would try it if someone could donate some Pd wires, or when I find the money to buy an ounce of Pd bullion.

[dangerousamateur]

The typical affect is to sensitize the composition, I'm told. I don't care to test the theory, so I'll purify the chlorate I plan to use.

 

Ok, but how does your purifikation process look like, if washing does not suffice?

 

Is my theory with the 2,5% right, or is there some fact I overloocked?

[WSM]

Ok, but how does your purifikation process look like, if washing does not suffice?

Is my theory with the 2,5% right, or is there some fact I overloocked?

 

If you wash the crystals with chilled DI water, you should loose very little chlorate. I prefer using a vacuum filtration set up and save the wash water to recharge with salt and use it in the next run of the cell.

 

The 2.5% should be the chlorate left in solution (if you calculated correctly). The rest of the chlorate will drop out as crystals as the temperature of the cell liquor drops or saturation occurs !!!

 

WSM

[WSM]

I don't really have a lot of money at the moment, and while Pd is cheaper (in fact much cheaper, like about 1/5th the price to be exact) it's still fairly expensive and not sold in gram bullions like Platinum. It's about 500 to 600 dollars an ounce at the moment, which compared to platinum is cheap. I guess I would try it if someone could donate some Pd wires, or when I find the money to buy an ounce of Pd bullion.

 

I expect if Pd worked, industry would have switched to it long ago. Pt does work, but it's cost is dear (and it gets slowly consumed in the process). Fortunately, platinum plating works and is much more economical than solid Pt (especially if you keep the chlorate levels up and avoid any chlorides in the cell, PLUS watch the power levels [not too high or too low]). Details, details, details...

 

WSM

[taiwanluthiers]

problem is I am even having trouble getting Pt plated anodes, because all I can find are those platinized titanium used for plating jewelries. Where can I get Pt plated anode with a thicker coating (I think the electroplating anode is only 2 microns, whereas it is preferred for Perchlorate anodes to have 20 microns)?

[WSM]

problem is I am even having trouble getting Pt plated anodes, because all I can find are those platinized titanium used for plating jewelries. Where can I get Pt plated anode with a thicker coating (I think the electroplating anode is only 2 microns, whereas it is preferred for Perchlorate anodes to have 20 microns)?

 

I don't know (off hand), but keep looking. Swede once mentioned that platinum clad titanium has a thicker coat than plated titanium (and is one thing industry uses [also platinum foil mounted to titanium frames]); maybe you could search for that (and if you locate some, please share the source and pricing with us!).

 

When I was searching for DSA anodes (MMO) several years ago, and found a distributor in my area, I acquired several samples including platinized niobium wire with a copper core. I still have it and never tried it. They suggested covering the end of the wire with epoxy to seal (and protect) the copper core. The epoxy won't hold up in the cell but I've conceived of a few different ways to use the wire as an anode in a perchlorate cell without exposing the copper core. If I can design a cell environment that won't eat the platinum, I may give it a try. I don't know if the platinized wire is still available, but if so, it was reasonably priced and not unaffordable. The OD is 1/16" (about 1.6mm) so the surface area is limited, it but if enough of it is used, it would work.

 

Swede and I are still working on a third alternative to platinum and LD. Stay tuned...

 

WSM

Edited January 26, 2013 by WSM

[taiwanluthiers]

just an idea, what about sealing the ends in glass tube?

 

About the LD plating method, I've read swede's blog about this but the way he did it, first soak it in Trtion X100, then the solutions (nitric acid with a huge cocktail of chemicals, some of which such as bismuth nitrate are expensive), and vacuum and spin jigs seems really costly and complex to do. It's hard to follow as to which one is absolutely necessary and which one is "nice to have" so is there a quick and dirty way of plating LD? I gather I need a power supply, some MMO (they said it was easiest to plate on top of MMO rather than bare titanium), beakers, lead and copper nitrate and nitric acids.

Edited January 26, 2013 by taiwanluthiers

[jholdswo]

I just received from Anomet, 4 Pt clad Ni wire mesh anodes. I have just jumped back into trying to produce a reliable pyro grade of Perchlorate since reviewing this forum and feeling a bit more comfortable with being able to determine the purity. I have always been very gun shy and treated all the product as chlorate. I am going to reproduce as best I can the collective work of many of the folks here for a POC to confirm Swede's and others work that a Pyro Grade Perc is possible for the average guy with smarts and a bit of resources as well as economical (largely will be based on the durability of the new anodes). I want to hold as many of the potential variables constant as possible and will be going the NaCl double decomp to get to KClO4. Plenty of pictures and I plan to video as well. I will start a blog to not impact the forums with a bunch of the same stuff already out there but I feel it important to confirm some of the awesome advancements made in the last few years by the very dedicated folks working this interesting challenge.

Since I have been out of production a while I really need to know was there ever any success with maintaining pH or temp inside the cell with respect to either % product achieved, purity or life of a platinized (or in my case clad) anode? And before you chastize me for not reading (I have scoured all the literature I could get my hands on) I have looked but not sure that there was ever anything conclusive as to the efficacy of qattemptoing to control pH or temp.

 

I would not like to recreate that effort or have to account for that as a variable that I need to control if possible. I will be mainly concerned with a viable cell design, process, reliable tests and reproducibility for the average science/pyro geek. Also, anyone have a line on N-Phenylanthranilic acid? I have one place in the UK (no takers in the US, you'd think I was asking for crack) offernig 25g for 235 US. Seems a bit much.

 

 

http://anometproducts.com//App_Themes/anometproducts/PtCladNb_Mesh.pdf

[taiwanluthiers]

How much was the Pt Clad anode?

[jholdswo]

There was a minimum order or 4 and they came out to $100.00 a peice total $400.00 for 2X6 Pt clad with a 5inch Ti lug spot welded. In retrospect I should have asked for Ti protection along the edge to protect the cut wire ends so the wire doesn't get eaten from inside out. Ughhhh it's always something .

[frank]

" In retrospect I should have asked for Ti protection along the edge to protect the cut wire ends so the wire doesn't get eaten from inside out. Ughhhh it's always something "

 

Relax!.

On page two of their catalogue (linked above) they state there is no exposed substrate. The wires are clad with Pt, including the

ends. They must cut the Nb (Niobium) wires first, then clad (including ends) and then weave. Nb is a valve metal anyways.

Thanks for the info. on price etc.

The wires are not electroplated with Pt but clad (however thats done?). I never realized cladding could be so thin.

 

edit:

I have just noticed you said Nickel substrate (with copper core coming from a different thread).

Are you sure its Nickle or is it Nb (Niobium)?

Edited February 9, 2013 by frank

[jholdswo]

LOL, guilty as charged on both counts. Thanks a bunch for the correction (not the first time I have been caught taking liberties with the periodic table)! I need to verify as the wire mesh from Anomet as indicated, really has a Cu core over Nb and then Pt clad. So if the ends are clad and that wears off it would possibly leave the Cu gooey center exposed.

 

I am trying to lay out a very detailed qualitative/quantitative series of trials. The real challenge is trying to do it part time, too bad it doesn't pay the bills. I haven't had to write up a lab report in a lot of years but I feel it's my turn to give something back and offer up what I intend to be an independent valiadation of the previous work done by the die hard enthusiasts. Thank goodness there are still some people out there still asking "Hmm...., I wonder, what if I.....".

 

While LD would still be the buffest of all anodes I am gonna' have to stick with Pt for now though. I long since gave up trying to do a homemade job from welding rod and hacked batteries, multiple washings and filtering through coffee paper etc.. This time around, lab glassware, a well regulated power supply (not bad mouthing the ATX those are fine too), temp and pH readings at regular intervals and strict controls..... More to come.

[taiwanluthiers]

LD is frustrating... you can't buy it from anyone so you have to make it yourself, dealing with toxic chemicals and needing more expensive equipments to do a proper job. It seems easier to just buy platinum.

[pyrojig]

I see that Im not the only one who has suffered the painful graphite mess. lol. Jholdswo : It seems like your on the right path. It is a learning curve, and sometimes one must "go through_to get to" the goods. I too have been long past the days of gouging rod produced kclo3. Gosh, what a mess that was . I too with the help of several pioneers, am jumping into the next wave of learning and great finds in the perch quest. It seems that working with a "tight" system electronically controlled is the only way to achieve a 90% CE. and a duplicateable set of results . I have been mixing a "simple cell ( 5gal W/BCA)" and a electronically controlled sys. to achieve a setup I hope will push into the 90%+ range. This will serve as a clean feed-stock for the next wave ( perch production!) . Follow the latest info on the perchlorates ,and the bucket cell- start to finish. There is some very new and exciting things being worked on behind the scenes.This will make for a cheaper/amateur produced electrode to get around buying expensive PT. Edited February 11, 2013 by pyrojig

[jholdswo]

This posting to forum stuff is kinda' tough as it seems like there exist many quite similar threads. I have officially decided to post here and have given up continuing my discussions on the "How to Make Perchlorate" thread. The nice thing is it appears that many of the same people are posting different places..... Many thank to all the folks that have already responded to my posts and given me some much additional to ponder and contemplate.

 

That said (and with thanks to WSM for his recent reply and suggestion) is there any reason not to try and conserve my precious Pt clad Nb wire anodes by running the classic double decomp of NaCl=>KClO4 by first running the cell with NaCl using CP Ti expanded mesh cathode and an MMO (Laserred eBay type for example) as an anode to avoid the Chloride/Pt conflict and switching to Pt anode and Ti cathode after substantial runtime enuring that a majority of NaCl has converted to NaClO3 and NaCl04? I have been writing up all the test cases and I am getting itchy to get going with some independent validation of the things that I have gleened from these pages but I would be a fool (my wife thinks I am already there) not to defer to the collective knowledge of this forum.

 

Thoughts or comments with the above before I mix up some super saturated NaCl sol'n and power on the 5V 35A power supply?

 

P.S. being a pragmatist and born skeptic I have to agree with Swede that if it was at all viable commercially the huge companies with nearly inexhaustable resources would be using anodic material other than Pt. If there is an MMO or LD magic bullet please find it soon so I can get this crazy idea of an amateur 90% plus efficient cell out of my head........

[taiwanluthiers]

If there is even a trace amount of chloride it seems it would cause pt anode to fail. I don't know if I want to go the sodium perchlorate route because I have no idea how to purify sodium chlorate, it is much more soluble than sodium chloride. Potassium chlorate on the other hand is easy to purify and it is still soluble enough at higher temperature to make a viable perchlorate cell.

[pdfbq]

The erosion of a Pt anode by the Cl^- ion is a bit exaggerated (I'm not saying its not there).

One day I wanted to make some KClO3 (for coloured smoke bombs) and put my Pt anode for one run in a saturated KCl soln. Did not do much damage.

 

Which brings me to the next point I have been thinking about.

To me it looks like the erosion of my Pt anode is not only because the Pt has been 'used' by the process. Also because it stops being attached to the Ti mesh.

 

 

Now maybe if you have Pt anodes for making Perc instead of for gold plating the Pt will stick better to the Ti.

 

I have no idea how much Pt is used in perc production without re winning of Pt. That would be nice to know.

Edited February 15, 2013 by pdfbq

[frank]

Platinum consumption for Na perk production runs at 2 to 7 grams per tonne. This is for cells using

sodium chlorate.

 

The problem with using Pt anodes that were meant for electroplating is that the coating of Pt is very thin. Any abuse at all

and you will soon run into problems.

 

 

"One day I wanted to make some KClO3 (for coloured smoke bombs) and put my Pt anode for one run in a saturated KCl soln. Did not do much damage."

 

Making chlorate with Pt is OK.

Its when Pt is used in a perk cell with some chloride in it is when you get Pt wear problems.

I have heard of Pt anodes (few micron of Pt on Ti) being destroyed after one or two batches of perk that were made by

running chloride all the way to perchlorate. Most of the wear will occur at the stage when the cell is at the inbetween stage of

chlorate/perchlorate. ie. a perk cell with chloride in it.

Why this happens was mentioned in some paper somewhere or other.

 

According to us patent attached Pt wear can be minimized by keeping the chlorate concetration in the perchlorate cell constant. In fact of the chlorate concentration is actually kept constant the erosion approaches zero. Hard to believe that one.

 

 

Regarding the picture of the anode above. Was it shiny (metalic pt) when new or some other colour? It does not look shiny from the picture.

[pdfbq]

According to us patent attached Pt wear can be minimized by keeping the chlorate concetration in the perchlorate cell constant. In fact of the chlorate concentration is actually kept constant the erosion approaches zero. Hard to believe that one.

Did you attach that patent? I have no clue how to seperate the NaClO4 from the NaClO3.

Regarding the picture of the anode above. Was it shiny (metalic pt) when new or some other colour? It does not look shiny from the picture.

This anode made about 10 kilo of NaPerc. Stil alive but worn. The color is Pt oxide. You get that when you run your cell to the end and the current goes up. I believe the Pt gets oxidized by th ozone then. If you put this anode in a new NaClO3 cell it gets silver again after a little while. Edited February 16, 2013 by pdfbq

[taiwanluthiers]

Is this one of those 75-100 microinch anode? I am contemplating getting one of those. Any idea how to rejuvenate an anode like this once it wears out? Can one just get some platinum bullion and use that to recoat it?

[frank]

Better luck this time with the attachement.

The patent is readly available from google anyways.

 

US 3475301 States that if Chlorate concentration in a Perchlorate cell is kept constant, the wear rate of he tPlatinum anode will approach zero.

 

@pdfbq

What type of Sodium Chlorate (I presume it's sodium you are using and not K?) are you using in the

Perchlorate cell. Is it home made or purchased (very pure). If it is homemade is there much or any Chloride in the Chlorate? Perhaps only a trace?

 

How many runs (approximately) have you done to make the 10kg. Or to put it another way what size is the cell.

 

Perhaps you have already answered all this above somewhere.

A full description of the cell would be great. Together with dept of Pt on anode, cost etc.

US3475301.pdf

[pdfbq]

If you had mentioned the patent number i would not have asked

 

I used Home made chlorate. Had one big Cell 30 liters and a Swede anode. Had it run for two moths.

Then boiled it down till solution gets clouded and NaClO3 precipitates out.

Wild guess would be 98% chlorate and 2% chloride what I used.

 

The cell is a 2.2 liter Ikea jar, dishwasher resistance.

I forgot a how many runs I exactly did. I believe I ended up with 1.25 kg of K perc for 1 run.

 

The anode is 5 X 13 cm from tyebangkok or something from ebay. about $85.

I was very lucky with the Ti, bought in gemany 1.5mm ti plates 30x25cm for 18 euro.

As you can see its not spot welded but clamped with some Ti strips.

I did run it on 5.2V computer power supply

 

Making perc is fast, I believe this cell finished in three days.

 

Attached some pics

 

Edited February 17, 2013 by pdfbq

[THEONE]

I have an idea for a cathode electron, you can easily get manganese dioxide from any carbon-zinc battery, so what it take a flat piece of wood-plastic aplay a layer of epoxy and on that layer add the manganese dioxide

[Mumbles]

I have my doubt if that will work, but why not try it and let us know?