making potassium (per) chlorate

[WSM]

Destroying chlorate in perchlorate solutions only makes sense if the amounts of chlorate are reasonaly small. You may have 10% ? 15% ? chlorate. This is far too much. Get an idea of how much chlorate you have. Take a small amount of the solution and evaporate to dryness and test the chlorate/perchlorate mixture by dropping some concentrated sulphuric acid on it. If you get ignition or alot of crackling you have TOO MUCH chlorate still present. Either run and run the cell (not advisable with platinum anode) using lead dioxide (if you have lead dioxide) or recrystallize.

A great way to get an idea of how much chlorate you have is to use Hydrochloric acid as a test on some of the diluted solution. See here for details (3 test tubes, down the page somewhat, with yellow colours showing)

http://oxidizing.typhoonguitars.com/chlorate/tests.html

Indigo carmine test here.

http://oxidizing.typhoonguitars.com/chlorate/so2pat.html[/url

More detail on indigo carmine test here

[url=http://oxidizing.typhoonguitars.com/chlorate/indigo.gif]http://oxidizing.typhoonguitars.com/chlorate/indigo.gif

There is no need to titrate chlortte solutions to get exact pH. No need for a pH meter either. The pH efficiency curve is quite blunt (as opposed to a spike) and the adding-acid/chlorine-escapeing thing is self regulating. Just add acid at the recommended rate.

I reviewed the various chlorate tests and I think a few that I haven't tried yet bear further investigation.

 

The trick will be accessing the reagents needed to try them.

 

WSM

[Arthur]

IF you can get the different oxidisers to selectively ppt out then all you need is to guesstimate the productivity of the perc stage and calculate to ppt out most to all of the perc leaving the chlorate in solution. This solution can be returned to the chlorate cell.

[WSM]

IF you can get the different oxidisers to selectively ppt out then all you need is to guesstimate the productivity of the perc stage and calculate to ppt out most to all of the perc leaving the chlorate in solution. This solution can be returned to the chlorate cell.

 

I suppose the trick is to not put too much KCl solution in.

 

If the runtime calculator is accurate enough, it would be a useful guide in determining when and how much KCl to add to the electrolyte.

 

We'll see...

 

WSM

Edited December 14, 2016 by WSM

[Arthur]

The patent I read said that the Kperc ppt out first, then KChlorate came out as a separate layer afterwards, SO putting 80% of the theoretical K content in should result in pure KPerc, Approaching 100% theoretical should give perc and then ClO3 in layers. Then more K should mean pure KChlorate. The trick is to determine the current efficiency of the second stage (by what level chlorate drops out) then working subsequent batches the same way.

[WSM]

The patent I read said that the Kperc ppt out first, then KChlorate came out as a separate layer afterwards, SO putting 80% of the theoretical K content in should result in pure KPerc, Approaching 100% theoretical should give perc and then ClO3 in layers. Then more K should mean pure KChlorate. The trick is to determine the current efficiency of the second stage (by what level chlorate drops out) then working subsequent batches the same way.

 

I see, so this discussion is appropriate for the future time (not too distant, I trust), when I have lots of NaClO₄ solution to deal with. Also, I see that besides all the other methods to determine chlorate presence, KCl solution may also be used (the crystal form showing the perchlorate and then the chlorate, in order).

 

This makes sense, but I need to try it in person and develop the skills, hopefully not wasting too much of my hard-won oxidizers in the process.

 

First, I need to create lots of sodium chlorate to experiment with (which is my current effort) and then convert much of it to sodium perchlorate solution. THEN, I'll have the chore of making chlorate-free potassium perchlorate from it.

 

Another observation is that I may be able to take a "back door" approach to determining the CE this way. Figure the CE by the chlorate appearance (by careful titration, I think) rather than prevent the chlorate appearance by (somehow) knowing the current efficiency. Hhmm, you may be on to something. I'll have to give this some more thought.

 

It may be simpler than I've been thinking, to see the difference between the crystal forms of the potassium perchlorate (fine, white crystalline powder) versus the potassium chlorate (large snowflake type crystals). I see I need to try this when I start making much more sodium perchlorate.

 

WSM

Edited December 15, 2016 by WSM

[WSM]

Upon closer inspection, my 6" heavy wall PVDF pipe section has one end cut square to the length and the other end is off by 1/4". In assembling the experimental high heat cell I first need to square cut the end of the pipe that's off. Also, I plan to use Viton gaskets, cut from flat sheet stock, between the PVDF pipe and the PVDF plate end caps, to afford a pliable and compatible, liquid-tight seal between the hard polymer parts.

 

Next I need to drill the 1/2" holes in the end plates for the threaded rod to pass through and tie the cell all together. The ends of the threaded rods need to be cleaned up where they were cut, with a slight chamfer so the stainless steel hex-nuts will go on and off smoothly. The heavy base plate needs to be drilled and tapped so the longer ends of the threaded rods can be threaded into it and secure the whole assembly into a functional unit.

 

After all that, the end plates need to be drilled and plumbed for the fittings which will hold the electrodes and sensors, plus plumb the fluids into and out of the cell.

 

After all of that is accomplished, the cell can be set up to run.

 

My thoughts are to use the depleted liquor from the sodium chlorate run last summer and recharge it with purified brine (as described in the patent) and run it till the liquor is reduced to 50% of it's starting volume, harvest the chlorate crystals that drop out at room temperature, recharge the electrolyte with more brine and run it again.

 

I plan to add in pH control and see if I can maintain the pH between 6.5 and 7.0 where I expect much greater efficiency in the runs.

 

WSM

Edited December 16, 2016 by WSM

[PTFE]

Hey guys..

If yome of you need PbO2 Anodes ask www.qixinti.com sales@qixinti.com

They've got 100x100x2mm Samples with terminal for 30$+shippment

[TomasBrod]

Hello all, just to report. Thank you for sharing pictures of your setup. I should share mine too, but stuff.

 

I am still struggling to get my mmo anode cell right. Last assembly was 3.5x10cm mesh and 1l jar. I started with saturated NaCl solution in distilled water and then followed the standard procedure of running a cell. Current was kept below 6A, voltage between 3.9V and 4.7V. I always kept a layer of undissolved salt at the bottom. I froze the liquor total 3 times, 3 days apart. After each freeze I topped up with saturated solution and added some solid salt. First one produced nothing (too early). Second and third produced enough of chlorate crystals. Then I forgot to add solid NaCl to the cell, I only added saturated solution and next morning current was near zero. And once dry the anode was lighter in color. I am starting to suspect that the mesh I purchased is somewhat low quality. Every small mistake and I am rewarded with one more good cathode. Aside: the small dimensions are due to space issues.

 

Do you think I am still missing something?

Edited December 18, 2016 by TomasBrod

[WSM]

Hello all, just to report. Thank you for sharing pictures of your setup. I should share mine too, but stuff.

I am still struggling to get my mmo anode cell right. Last assembly was 3.5x10cm mesh and 1l jar. I started with saturated NaCl solution in distilled water and then followed the standard procedure of running a cell. Current was kept below 6A, voltage between 3.9V and 4.7V. I always kept a layer of undissolved salt at the bottom. I froze the liquor total 3 times, 3 days apart. After each freeze I topped up with saturated solution and added the undissolved salt. First one produced nothing (too early). Second and produced enough of chlorate crystals. Then I forgot to add solid NaCl to the cell, I only added saturated solution and next morning current was near zero. And once dry the anode was lighter in color. I am starting to suspect that the mesh I purchased is somewhat low quality. Every small mistake and I am rewarded with one more good cathode. Aside: the small dimensions are due to space issues.

Do you think I am still missing something?

 

Hi Tomas,

 

Without more information, it'll be hard to tell. What is the source of your MMO anodes? I apologize if you've already told us, I've been in contact with so many different people here that keeping straight "who is doing what" is getting difficult for me.

 

The numbers you quote sound reasonable and with the MMO I'm using, I wouldn't expect any such problems. The fact that you're MMO is breaking down makes it sound suspect, or there's some aspect of your setup or other conditions that we're missing.

 

Let us know, when you get the chance.

 

WSM

Edited December 19, 2016 by WSM

[WSM]

Hey guys..

If yome of you need PbO2 Anodes ask www.qixinti.com sales@qixinti.com

They've got 100x100x2mm Samples with terminal for 30$+shippment

 

Thanks, PTFE.

 

I emailed them an inquiry and will post their response and whether they're amenable to dealing with small orders from individuals. We'll see...

 

WSM

[WSM]

For those interested, I just noticed a new posting on pyrobin (www.pyrobin.com) which contains the entire contents of the book, "Chlorine and Chlorine Products" circa 1915. It's an interesting historical reference with details of how it was done a hundred years ago.

 

The title sounded familiar so I checked my library and found I acquired a hard copy of the second printing (1918) in May 2005 from a bookseller in the UK. Still, it's good to have a digital copy I can carry with me in a small thumb drive.

 

WSM

 

Edit: the link is http://www.pyrobin.com/files/chlorinechlorin00clougoog.pdf

Edited December 21, 2016 by WSM

[WSM]

I've been thinking about various options for chlorate cell designs and realize there are many different configurations that will work. The best one in any situation is the one you can manage to do with the materials available to you at the time you do it.

 

 

Happy Winter Solstice, to those of us in the Northern hemisphere (and Happy Summer Solstice to the rest of us).

 

WSM

Edited December 22, 2016 by WSM

[WSM]

Destroying chlorate in perchlorate solutions only makes sense if the amounts of chlorate are reasonaly small.

 

Actually, destroying the chlorate in sodium perchlorate solutions makes perfect sense if your goal is chlorate-free, high purity perchlorates.

 

As for methods NOT requiring the chemical destruction of chlorates, I like the idea of selectively crystallizing out the potassium perchlorate before any chlorate begins to form (as Arthur shared). The trick is to know, or at least have an educated guess as to the CE, to accurately separate the two.

 

The metabisulfite destruction of chlorate in the perchlorate electrolyte, works, is inexpensive and the byproducts are soluble after the KCl is added to drop out the potassium perchlorate; making cleanup of the desired product an easier task.

 

Still, testing for the presence of chlorate is required, and a compatible test is essential.

 

WSM

Edited December 24, 2016 by WSM

[WSM]

I'm still working on the experimental, high temperature cell. Work on it is slow because of all the things happening to prepare for Christmas. The first hurdle is squaring the crooked, cut end of the PVDF pipe. Since it's heavy walled, nearly three feet (~89 cm) long and weighs nearly 10 Kg, it's a bit unwieldy to handle.

 

I'll start taking photographs and share them so everyone can appreciate the challenges I'm facing. I won't let the difficulties stop me, but for the time being, my progress will be slow.

 

More later...

 

WSM

[PTFE]

Hey wsm,

Im pretty interessted in your Hightemp. cell.

At the moment my little cell is running for the first time.

The one, with the Electrodes i shown before.

Its working pretty well i guess, its also working at high temperatures.

At 4,5Volts it takes 55Amps and the Temp is rising to 91°C.

The cell can handle 1,5litres and i started with 400g Nacl, adding about 1L saturated solution per day to top it up.

I just dont know how long i will let it run this time, but i think, i will wait until naclo3 drops out.

Tomorrow i can give you some pictures if you are interessted.

[WSM]

Hey wsm,

Im pretty interessted in your Hightemp. cell.

At the moment my little cell is running for the first time.

The one, with the Electrodes i shown before.

Its working pretty well i guess, its also working at high temperatures.

At 4,5Volts it takes 55Amps and the Temp is rising to 91°C.

The cell can handle 1,5litres and i started with 400g Nacl, adding about 1L saturated solution per day to top it up.

I just dont know how long i will let it run this time, but i think, i will wait until naclo3 drops out.

Tomorrow i can give you some pictures if you are interessted.

 

Yes, me too.

 

At this point, I'm gathering the various components and planning the assembly of them. Today, after a Christmas party at work, I took the main tank pipe to the workshop at work and cut the end square. I also managed to buy two 10 foot lengths of 1/2" PVC pipe to cover the threaded rod, which binds the whole assembly together, vertically.

 

I look forward to seeing the photographs or videos of your setup and the yield.

 

WSM

Edited December 24, 2016 by WSM

[WSM]

I'm still working on the experimental, high temperature cell. Work on it is slow because of all the things happening to prepare for Christmas. The first hurdle is squaring the crooked, cut end of the PVDF pipe. Since it's heavy walled, nearly three feet (~89 cm) long and weighs nearly 10 Kg, it's a bit unwieldy to handle.

I'll start taking photographs and share them so everyone can appreciate the challenges I'm facing. I won't let the difficulties stop me, but for the time being, my progress will be slow.

 

I arranged and took a photo of the main tank pipe and the end cap plates.

 

 

The wall thickness of the pipe is nearly 12 mm (about 0.470"), the bottom plate is roughly 19 mm thick (0.750") and the top plate close to 9.5 mm thick (0.375"). I plan to use four 4' (~1.2 m) lengths of 1/2" (12.7 mm) stainless steel threaded rod with stainless steel nuts and flat washers to tie the PVDF parts together. I'm thinking of covering the threaded rods with white PVC plumbing pipe so the sharp edges of the threads won't be exposed, when the tank is assembled.

 

I plan to keep the tank closed and plumb the fluids through from a holding tank. I'll firm up these plans after the tank assembly is put together and leak tested. My thought is to have the extra length of the threaded rods extend below the vertical tank and screw them into a heavy steel base plate, allowing enough space between them for plumbing fittings on the bottom of the tank.

 

Once it's all together and plumbed, I need to do a trial run and fine-tune the power required to get the temperature up to between 105^oC and 110^oC, for the proper operation of the cell as designed.

 

WSM

Edited December 25, 2016 by WSM

[WSM]

Well, this has been a long (productive) day. I got into the workshop this morning and started getting ready to assemble the high temperature tank and as the day wore on I got further and further along till the basic tank was completed this evening.

 

 

This tank assembly with the stand is about 4 feet (1.22 meters) tall.

 

I still need to disassemble it so I can add in Viton gaskets and prepare the top and bottom plates by drilling & tapping them for plumbing with compatible fittings. There's a lot to do but maybe I can make some headway by New Year's day, and start next year by running the new experimental cell (which would be nice if I can manage it within a week). We'll see...

 

WSM

 

Edit: Happy Christmas Eve !

Edited December 25, 2016 by WSM

[Arthur]

Best wishes with the project. Do find somewhere for the hydrogen to vent out safely.

[WSM]

Best wishes with the project. Do find somewhere for the hydrogen to vent out safely.

 

Thank you, Arthur.

 

The venting of hydrogen will have to be combined with the recirculation of water released as vapor from the hot cell (in lieu of refluxing it back into the cell, like the previous experiment). I'm working on various methods to accomplish all this, but I appreciate any and all suggestions.

 

This assembly can survive outdoors as well as inside. Also, it's a shell and needs much more work before it'll be ready for service, but in this form it shows the potential to be a workhorse.

 

If any of you have questions about the details of this RC (reaction chamber) tank or my ideas for it's application, feel free to ask. I'll answer here for the benefit of all.

 

Thanks to you all, and have a very, MERRY CHRISTMAS .

 

WSM

Edited December 25, 2016 by WSM

[WSM]

Happy Holidays to All, and may the New Year be happy and bring prosperous times to all of us.

 

Regards, WSM

Edited December 25, 2016 by WSM

[greenlight]

Happy holidays to you to WSM....

 

I have received the meter and shunt to monitor the cell finally. Before I wire it up I just wanted to see if anybody can tell me I have it right as I am not the best with electronics.

Attached is a the diagram of how I understand it is all connected.

Edited December 27, 2016 by greenlight

[WSM]

Happy holidays to you to WSM....

I have received the meter and shunt to monitor the cell finally. Before I wire it up I just wanted to see if anybody can tell me I have it right as I am not the best with electronics.

Attached is a the diagram of how I understand it is all connected.

 

It looks good at first glance but doesn't the seller have a wiring diagram you can work from? Most sellers of these meters have a diagram you can download and print out. I would be certain before wiring it up because some of these meters are very sensitive to wiring in reverse polarity (I've destroyed a couple, unfortunately ).

 

Can you post a photo of the connection side of the meter? Maybe that would help determine if the diagram is correct.

 

One test I've done is to connect power to the meter, just to see if the display comes on. It may be important to first identify the power input and distinguish it from the sensor input.

 

Good luck, greenlight.

 

WSM

[WSM]

Happy holidays to you to WSM....

I have received the meter and shunt to monitor the cell finally. Before I wire it up I just wanted to see if anybody can tell me I have it right as I am not the best with electronics.

Attached is a the diagram of how I understand it is all connected.

 

I just gave the Chinese made dual voltage/amperage meter on eBay another look. If you have the model D85-3051, your drawing is the correct one. That wiring scheme is for the meter connected to voltages below 40 Vdc with an external shunt (as opposed to the other three drawings).

 

I think you're on the right track. Good luck with it.

 

WSM

[WSM]

I pulled the cell assembly apart so I could clean up the top end of the main tank body (which was cut slightly uneven) to match the now straight bottom end; also I cut two gaskets from some 1/16" (0.0625" or about 1.6 mm) black Viton sheet stock I bought on eBay, a few years ago.

 

 

I realize that I need to decide what size electrodes I need to build, to run the cell hot enough to work properly (I have enough anode material that I can make them any size I want). I'm not sure yet how big to make them, but I'm working on the answer.

 

My thinking is that I'll build the electrodes and mount them in the bottom of the cell before I reassemble the tank, over them. I'll also drill and tap several other ports in both the top and bottom plates for various fittings and accessories. I'll either put those fittings in place or plug the ports till they're needed, later on; before I reassemble the cell.

 

To determine the fluid level, since the pipe is translucent white plastic, I'm considering backlighting the cell with a bright white automotive LED strip light designed for daytime run lights on cars. It ought to allow a view of the liquid level in the tank. We'll see... (pardon the pun)

 

Once I determine the appropriate electrode sizes, I'll build them with heavy walled 1/2" (12.7 mm) CP titanium tubing leads, filled with solid copper rods for conductivity. I'll thread the ID of the tube on the opposite end from the electrodes and use stainless steel hex bolts and washers to connect the power cable lugs for power to the electrodes. I'll mount the titanium lead tubes in modified PVDF compression fittings in the bottom of the cell, so the lead lengths can be shorter than they'd otherwise be if mounted in the top of the cell.

 

There's much more work to do but I'm pushing forward to get this going.

 

WSM

Edited December 30, 2016 by WSM