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making potassium (per) chlorate


gods knight

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Actually it kinda remind me of a Quora question where some guy asks if a foreign army invades the US will the armed civilians be able to defend it. One answer basically said that if the US were to be invaded, then something terrible has happened that the US military was unable to stop a foreign invader, and that the enemy force would be far too powerful that civilian defense of the country would be literally impossible..

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I don't know, fiddleguy... 35 to 100 million armed citizens sounds like a pretty daunting 'defense force' to me!

 

As has often been MISattributed to Japanese Admiral Yamamoto -- "You cannot invade the mainland United States -- There would be a rifle behind every blade of grass".

 

Lloyd

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Well, he still has a point. If someone is able to pacify the US fighting forces, i'm not entirely convinced that the general population could actually put up much of a fight. But that is mostly since i see the current US armed forces as pretty much "the" milestone to beat. If they instead were, lets say, bound to inacivity through treason, or what ever, then perhaps it all comes in a different view. But that is just never going to happen.

 

I guess the real question is... Could the US armored forces defeat the general population if they were to be opposing forces at some point? I hope not.

B!

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You know, the faster we get back to discussing the electrochemical synthesis of chlorates and perchlorates, the faster those very hypothetical situations will be rendered a non-issue. :)

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You know, the faster we get back to discussing the electrochemical synthesis of chlorates and perchlorates, the faster those very hypothetical situations will be rendered a non-issue. :)

 

You're right.

 

WSM B)

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I just checked the experimental sodium chlorate cell. It's run 744 hours so far, at an average of about 45A; so I estimate the total of 33480 Ah, which is about 1240 Ah/liter. I wish I could remember how many Ah are required to convert the bulk of my NaCl to NaClO3, but I just got back from an eye exam by the opthamologist and my eyesight is wonky from the dilation drops he put in, so it'll have to wait :wacko: :mellow:.

 

Maybe it's time to chill a small sample of the electrolyte again? I'd better do it later... :whistle:

 

WSM B)

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"You know, the faster we get back to discussing the electrochemical synthesis of chlorates and perchlorates, the faster those very hypothetical situations will be rendered a non-issue. "

 

-------------

Mumbles, having read (actually) hundreds and hundreds of posts about this over the decades, and never finding anyone who'd actually been satisfied with electrode erosion OR the volume of production, or purity, or yield... you name it... then,

 

I'd say the 'diversion' subject was just about as informative about the subject as all this other endless banter about something nobody can seem to make work reliably!

 

:D

 

Lloyd

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

WSM I hope this might be of help. It is a quick search in my notes and saved sites .

 

Thanks, pyrojig. I actually have it, but when I read it again (correcting the typos as I went), something struck me about how I could use the numbers to estimate the yield.

 

I'll look at it again after work and see if it works for me (of course I'll be tired by then, but we'll see...).

 

WSM B)

Edited by WSM
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I just checked the experimental sodium chlorate cell. It's run 744 hours so far, at an average of about 45A; so I estimate the total of 33480 Ah, which is about 1240 Ah/liter. I wish I could remember how many Ah are required to convert the bulk of my NaCl to NaClO3, but I just got back from an eye exam by the opthamologist and my eyesight is wonky from the dilation drops he put in, so it'll have to wait :wacko: :mellow:.

Maybe it's time to chill a small sample of the electrolyte again? I'd better do it later... :whistle:

WSM B)

 

Okay, so I took reads this morning and decided to take a small sample and chill it. It will sit at about 5oC till I get back in about 11 hours. The hours of running were 756 which is about one full month.

 

Visually, it's hard to tell what's dropping out because sodium chloride and sodium chlorate look about the same. Testing is required. Due to the temperature differences, chlorate should drop out and chloride stay in solution. We'll see...

 

WSM B)

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Okay, so I took reads this morning and decided to take a small sample and chill it. It will sit at about 5oC till I get back in about 11 hours. The hours of running were 756 which is about one full month.

Visually, it's hard to tell what's dropping out because sodium chloride and sodium chlorate look about the same. Testing is required. Due to the temperature differences, chlorate should drop out and chloride stay in solution. We'll see...

WSM B)

 

I let the sample sit between 0oC and 5oC for 48 hours and the sodium chlorate crystals grew continuously for all that time till I have a small collection of jewels.

 

post-9734-0-75994800-1467288705_thumb.jpg post-9734-0-06279400-1467290799_thumb.jpg

 

The largest is roughly 6 mm (1/4") square. I'm a little surprised, but it makes sense that the crystals would continue to grow as they sit in the concentrated liquor at reduced temperatures where they want to drop out of solution.

 

I poured the depleted liquor back into the cell and kept the chlorate sample (my jewels) to dry and analyze. This is very cool!

 

WSM B)

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wsm those crystals are larger than anything I have made . it sure looks good .... what is the purity ?

 

 

memo.

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wsm those crystals are larger than anything I have made . it sure looks good .... what is the purity ?

memo.

Thanks, memo. I don't know the purity yet but I suspect it's probably pretty good (crystallization is nature's way to purify things).

 

I'll see if I can test the crystals after work today.

 

WSM B)

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What size of sample did you take to get those crystals? What sort of yield from the whole cell does that sample indicate?

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How do you test them to determine whether they're chloride or chlorate crystals?

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What size of sample did you take to get those crystals? What sort of yield from the whole cell does that sample indicate?

 

The sample of electrolyte was approximately 350 ml or about 1/77 of the whole volume; figuring a 27 liter cell volume. I'm still running the cell but need to keep adding NaCl to keep saturating the electrolyte with NaClO3. This is still the first run, even though it's semi-continuous.

 

WSM B)

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How do you test them to determine whether they're chloride or chlorate crystals?

 

The crystals are still moist with electrolyte but hopefully they'll dry out soon.

  • Once they're fully dry, dissolve a small sample in distilled water.
  • Place several portions in different test tubes or depressions in a spot plate.
  • Test one with a silver nitrate solution. A white precipitate (silver chloride) is indicative of chloride.
  • Either the classic Indigo Carmine test or the NPAA test used by Swede would quickly determine if chlorate is present.

Using both tests should help determine if a mixture is present and which one is dominant or if rinsing (purification) of the product is called for.

 

I suppose for grins, I could mix a little granulated sugar with a couple smaller crystals and apply the flame of a propane torch and see what happens :P!!! (Maybe I will ;))

 

WSM B)

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Gorgeous crystals! Those belong on gold rings!! :)

 

A tempting thought if they weren't soluble in water.

 

Thanks.

 

WSM B)

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I suppose for grins, I could mix a little granulated sugar with a couple smaller crystals and apply the flame of a propane torch and see what happens :P!!! (Maybe I will ;))

WSM B)

 

Okay, I just did; and even moist plus with very coarse crystals, it burned slowly (but positively) with a distinct yellow flame. Any doubts about the crystals being sodium chlorate have been removed from my mind.

 

I'm certain if the crystals were fully dried and ground to a fine powder, and then mixed with powdered sugar (or some other appropriate fuel), they'd have gone "poof" instead of "sizzle".

 

More to come...

 

WSM B)

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Okay, I just did; and even moist plus with very coarse crystals, it burned slowly (but positively) with a distinct yellow flame. Any doubts about the crystals being sodium chlorate have been removed from my mind.

 

I'm certain if the crystals were fully dried and ground to a fine powder, and then mixed with powdered sugar (or some other appropriate fuel), they'd have gone "poof" instead of "sizzle".

 

More to come...

 

WSM B)

Excellent!

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A good friend and fellow electrochemist shared some writings of dann2 (on sciencemadness) from around 2008, on the subject of harvesting sodium chlorate. Also a run length calculator from Alan Yates. From those documents, he estimates my sodium chlorate experiment's first run may be complete.

 

I decided that since the latest sample (the jewels) looked so nice, I'd try a larger sample. On the evening of July 1st, I put about three liters of the cell electrolyte in a PET jar with a lid and put it in the fridge set to between 0oC and 5oC. So far the crystals are beginning to grow nicely. I'm tempted to let them grow for a bit longer than last time and see how big they can get.

 

Rather than harvest NaClO3 from all of the electrolyte, I'm considering adding solid NaCl and continuing the run. I believe the best chance for getting concentrated NaClO3 in the electrolyte is to keep adding NaCl till the chlorate levels rise to at least 600g/l in the mother liquor.

 

After I get the system settled and producing regularly, I plan to add pH control by periodic additions of dilute HCl. The goal is a pH of 6.8 or as close as I can manage.

 

WSM B)

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The sample of electrolyte was approximately 350 ml or about 1/77 of the whole volume; figuring a 27 liter cell volume. I'm still running the cell but need to keep adding NaCl to keep saturating the electrolyte with NaClO3. This is still the first run, even though it's semi-continuous.

WSM B)

 

Using the results of the first sample of sodium chlorate crystals harvested, I calculate the amount of crystals I should be able to collect from this first run to be about 8.5 pounds (about 3.85 kilos). If I then saturate the depleted mother liquor with sodium chloride, the next run should yield a larger crop of NaClO3 crystals.

 

This is because I'm starting with liquor full of precursor ions, including chlorate and sodium ions in the solution. It ought to make a decent crop, even without pH control. With pH control, even more NaClO3 and with less power consumption.

 

I have a lot of work to do... :whistle:

 

WSM B)

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I harvested the larger batch of crystals from the 3+ liter jar late this morning:

 

post-9734-0-82813500-1467658595_thumb.jpg

 

This photo shows the crystals on a 24 cm filter paper. They're still wet with electrolyte so I won't weigh them till they're completely dry. The largest single crystals are almost 1 cm square and completely clear, but most are between 16 mesh and 4 mesh.

 

The left over depleted electrolyte is sitting with new salt crystals in the bottom of the jar. I'm thinking about putting a magnetic stir bar in and stirring it till the salt completely dissolves, then add it back into the cell after filling another jar with hot electrolyte and putting it into the fridge.

 

WSM B)

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