making potassium (per) chlorate

[abbykarim]

At room temperature, some chlorate is soluble. See if you can get the solubility chart which compares the various chlorides, chlorates and perchlorates at different temperatures, to get the relative solubilities. By this you can determine which temperature to aim for for different results.

 

If your agricultural potash is white, I wonder if it's chloride or carbonate? Where is it found (what Country)?

 

WSM

im from trinidad. i do landscaping and so i get to use lots of fertilisers. till recently i managed to check with one importer of white potash and the chemical info stated 95% kcl, so i am hoping it it what it is...other wise i havent been able to locate any kcl water softener.

 

if in the video i posted above, it is a combination of perchlorate and chlorate, or if it is even pure chlorate, is there a good method of going to the perchlorate form......like boiling with h2o2?

 

 

i really need to get this right, i have already bought my self a platinum coated titanium electrode, ss anodes, broke my pc to get my power supply, plan on breaking a friends pc to get his...

 

....

MrB, I am in no way an authority on any of this. I run my cells at 55 to 65c continually. Everything that I produce has been KCLO3 until 2 weeks ago when I accidently ran from KCL to KCLO4 for the first time. It took my cells 9 to 10 days to produce 95% KCLO4 with the rest being KCLO3. I only run the cells at 5vdc @ 13a though. There was some fiber/string like substance that dropped out of solution first, you can see the story on page 149, and I still do not know what they are.

even thunder got to go from kcl straight to klo4........can you determine the change to your set up that made this happen?

[schroedinger]

If you allready got a platinum electrode, your best shot is to get NaCl and an MMO or MnO2 electrode and do sodium chlorate with it. Then use the platinum electrode to go for sodium perchlorate. After that destroy the chlorate left over with metabisulfite and add kcl solution. Than nearly chloride free pattasium perc will drop out. Recristallize from distilled water and you will be chloride free.

[abbykarim]

 

 

 

If you allready got a platinum electrode, your best shot is to get NaCl and an MMO or MnO2 electrode and do sodium chlorate with it. Then use the platinum electrode to go for sodium perchlorate. After that destroy the chlorate left over with metabisulfite and add kcl solution. Than nearly chloride free pattasium perc will drop out. Recristallize from distilled water and you will be chloride free.

 

i saw the video above, im assuming he used a platinum anode a stainless steel cathode and ran the concentrated NaCl for 5 days thus producing the NaClO4 .......then boild down the electrolyte to concentrate the per chlorate?....then fused the kcl wich made the less soluble KClO4 which fell from solution?

[MrB]

i saw the video above, im assuming he used a platinum anode a stainless steel cathode and ran the concentrated NaCl for 5 days thus producing the NaClO4 .......then boild down the electrolyte to concentrate the per chlorate?....then fused the kcl wich made the less soluble KClO4 which fell from solution?

From looking at the video he boiled it just to make any hypochlorite go away. He doesn't say anything about keeping on boiling it to reduce the volume, so i suspect he cuts the batch in half simply for the reason that he hasn't got a 10L glass beaker. But thats just me, without actually understanding the chemistry behind it.

B!

Edited August 21, 2014 by MrB

[WSM]

 

i saw the video above, im assuming he used a platinum anode a stainless steel cathode and ran the concentrated NaCl for 5 days thus producing the NaClO4 .......then boild down the electrolyte to concentrate the per chlorate?....then fused the kcl wich made the less soluble KClO4 which fell from solution?

 

Having just watched the video, my impression is he's making chlorate, not perchlorate here. The crystal type and structure looks like chlorate.

 

If he added the KCl solution to sodium perchlorate, I'd expect an immediate dense cloud of fine perchlorate crystals to appear and slowly drop to the bottom of the vessel.

 

The proof of perchlorate presence is to add a drop or so of methylene blue solution to a small sample solution and look for a change of color from blue to purple (positive for perchlorate). The time to develop is very fast for higher concentrations or much longer for weak concentrations.

 

WSM

[abbykarim]

from what i was reading he is correctly making perchlorate, some reading suggest that the electrolyte be boiled with the addition of some hcl as this would also remove the chlorate molecules present i the solution, then addition of sodium hydroxide to bring the solution back to a neutral state since perchlorate in acid state is very unstable. they also recommended boiling the electrolyte down to half the volume to concentrate the perchlorate...

[pex]

I lookt at that movie a few Times to. And I understand what WSM means. The cristalls falling down look like chlorate. I did this reaction many times. To make kclo3. And the shape of the chlorate cristalls. Look the same. Perchlorate cristalls are a lot smaller. I think that he made perchlorate with a lot chlorate left in it. Methyleen bleu is a good test. To see of perchlorate starts to form. Indigo is the way to go.

[pex]

The easyest way to clean your perchlorate is to use sodium metabisulfite. I did this a few Times. Start with a smal amount. Heat the solution to Boiling point. Take a sample and test it with indigo. When there is still clorate left in the solution. Do the first step again. When its gone. Take your kcl solution. let it cool down and rinse it with chilled demi water till the sodium metabisulfite smell is gone. There is your pure perchlorate

[WSM]

The easyest way to clean your perchlorate is to use sodium metabisulfite. I did this a few Times. Start with a smal amount. Heat the solution to Boiling point. Take a sample and test it with indigo. When there is still clorate left in the solution. Do the first step again. When its gone. Take your kcl solution. let it cool down and rinse it with chilled demi water till the sodium metabisulfite smell is gone. There is your pure perchlorate

Hi pex,

 

I noticed that you and I are making the same mistake. We're both being unclear about some details that can mislead others if we're not careful.

 

We should spell out exactly what we're using and how. For example, when you specify using sodium metabisulfite to break down residual chlorate, I'm certain you're referring to a sodium perchlorate cell. Maybe we should specifically state that in our descriptions for clarity.

 

What does everyone think about this?

 

WSM

I'm not throwing stones here, it's clear that I'm doing the same thing. I'm saying we should try to do better so others aren't mislead.

Edited August 27, 2014 by WSM

[schroedinger]

Well I'm pretty sure it can't hurt to do so. Even if everyone who attempt this should know when it gets used.

Btw. would it be possible to use the bisulfite after adding the pottasium?

[WSM]

Well I'm pretty sure it can't hurt to do so. Even if everyone who attempt this should know when it gets used.

Btw. would it be possible to use the bisulfite after adding the pottasium?

 

I don't know, but I think it should work (even if it's not recommended).

 

One thought though, if using metabisulfite to break down chlorate, I recommend using it before it has the potassium chloride added (which I believe is the usual method). Also, use sodium metabisulfite in a sodium perchlorate cell and potassium metabisulfite in a potassium perchlorate cell.

 

Even if the ultimate goal is potassium perchlorate, I think it's perfectly permissible to use sodium metabisulfite in a sodium perchlorate cell, before exchanging with potassium chloride to convert the sodium perchlorate to potassium perchlorate. Any residual potassium or sodium salts left after the chlorate removal with either type of metabisulfite and the KCl exchange, should be soluble and wash away from the much less soluble KClO₄.

 

WSM

Edited August 28, 2014 by WSM

[abbykarim]

has anyone ever come up with a down right simple and straight foward reaction to make pure perchlorate without using lots of chemicals...my problem is that access to certain chemiclas is going to be tough

[WSM]

has anyone ever come up with a down right simple and straight foward reaction to make pure perchlorate without using lots of chemicals...my problem is that access to certain chemiclas is going to be tough

 

The answer is yes, but you won't like it:

 

HClO₄ + KOH --> KClO₄ v + H₂O

 

If it were easy, everyone would be doing it.

 

WSM

[WSM]

Well I'm pretty sure it can't hurt to do so. Even if everyone who attempt this should know when it gets used.

Btw. would it be possible to use the bisulfite after adding the pottasium?

 

If this situation faced me, I'd lean toward using potassium metabisulfite, rather than introduce any sodium salt into my potassium perchlorate solution.

 

WSM

[WSM]

I lookt at that movie a few Times to. And I understand what WSM means. The cristalls falling down look like chlorate. I did this reaction many times. To make kclo3. And the shape of the chlorate cristalls. Look the same. Perchlorate cristalls are a lot smaller. I think that he made perchlorate with a lot chlorate left in it. Methyleen bleu is a good test. To see of perchlorate starts to form. Indigo is the way to go.

 

To be clear:

 

Indigo Carmine tests for chlorate

Methylene Blue tests for perchlorate

 

Also, I've used three different tests for chlorate and, unfortunately, none of them are stable enough to last much over a month when the reagent is prepared. Methylene blue, on the other hand IS stable and will last for years after it's prepared.

 

WSM

[WSM]

If you allready got a platinum electrode, your best shot is to get NaCl and an MMO or MnO2 electrode and do sodium chlorate with it. Then use the platinum electrode to go for sodium perchlorate. After that destroy the chlorate left over with metabisulfite and add kcl solution. Than nearly chloride free pattasium perc will drop out. Recristallize from distilled water and you will be chloride free.

 

I agree. Plus I see laserred is still offering low cost MMO on eBay (even though he's raised his prices, his MMO is the lowest cost material out there).

 

Check item number 351156948585

 

WSM

[WSM]

im from trinidad.

even thunder got to go from kcl straight to klo4........can you determine the change to your set up that made this happen?

 

I imagine the main drivers are:

 

The chlorides were down to an "acceptable" level

Enough chlorate was still in solution

The voltage, current and temperature were high enough

The platinum anode had the right oxygen overpotential (till everything, PLUS the chloride level killed the platinum coating)

 

When thunder described his platinum anode as having yellow patches, that indicated to me the platinum was nearly gone and the titanium substrate was attacked and reacted to form the yellow titanium salt observed.

 

That's my best guess, anyway.

 

WSM

[jpsmith123]

has anyone ever come up with a down right simple and straight foward reaction to make pure perchlorate without using lots of chemicals...my problem is that access to certain chemiclas is going to be tough

 

Based on some things I've read (like this) I sometimes think that if boron-doped-diamond (BDD) anodes ever become available at a reasonable price, then we might finally have a "simple and straightforward" [although still electrolytic] process to go directly from chloride to perchlorate with high efficiency and complete or almost conversion of Cl to ClO4. With this material, it might even be practical to convert HCl directly to HClO4.

 

Actually we may be able to make our own BDD anodes right now because I just found a place selling BDD nanopowder - which could be electrophoretically deposited onto various substrates. I've often thought that an electrophoreticlly deposited BDD layer on platinum or MMO or something would be the "Holy Grail". I was going to start experimenting soon with Bismuth compounds, but the availability of BDD nanopowder at a price of 5 grams for $65 gives me pause.

[schroedinger]

Did anyone ever tried glass carbon electrodes? They whould work, they get used for making persulfate which requires a higher oxygen overpotental then perc does. Only platinum, pbo2 or glass carbon are suited for this task. Also the interesting thing is that it persulfate cells it gets operated at really high amperes.

[jpsmith123]

IIRC, someone tried glassy carbon (for perchlorate) over at sciencemadness...to no avail.

 

Speaking of glassy carbon, that was one of the things that's been used as a substrate for "mechanically attached" Bi2O3, although AFAIK it was never tried for perchlorate.

 

I've always wondered how glassy carbon with "mechanically attached" BDD powder would work as a perchlorate anode.

[abbykarim]

keep me posted when you guys score................

[WSM]

I've often thought that an electrophoreticlly deposited BDD layer on platinum or MMO or something would be the "Holy Grail". I was going to start experimenting soon with Bismuth compounds, but the availability of BDD nanopowder at a price of 5 grams for $65 gives me pause.

 

Where?!! Please share

 

WSM

Edited August 31, 2014 by WSM

[Arthur]

Lets say that BBD powder at 5g for $65 is a LOT cheaper than platinum.

 

Perc is now on "lists" in the UK, and hard to buy, most European countries will ban it's private sale soon.

[WSM]

Lets say that BBD powder at 5g for $65 is a LOT cheaper than platinum.

Perc is now on "lists" in the UK, and hard to buy, most European countries will ban it's private sale soon.

 

Getting the powder permanently attached to an electrode is going to be the greatest challenge. Even the manufacturers of BDD electrodes admit that the coefficient of thermal expansion between BDD and substrate materials, and the internal stresses of the electrode is one of the greatest hurdles to overcome.

 

No one is discussing what the actual cost of a useable electrode will be. So far, platinum or lead dioxide are looking MUCH more atractive (and available).

 

As for Bi₂O₃ electrodes, has anyone put forth ANY evidence of their utility for perchlorate production? Theory is fine, but useless for practical application till proven.

 

The ability of individuals to access perc in the UK as well as the EU may well foreshadow a similar situation in the United States as well as other parts of the globe if political situations continue on their current apparent course. The only obvious solution is to produce it yourself to supply your research needs. Though this will avoid the "private sale" ban, the problem still exists if private posession is banned.

 

What's a pyrotechnics enthusiast to do?

 

WSM

[jpsmith123]

 

Getting the powder permanently attached to an electrode is going to be the greatest challenge. Even the manufacturers of BDD electrodes admit that the coefficient of thermal expansion between BDD and substrate materials, and the internal stresses of the electrode is one of the greatest hurdles to overcome.

 

 

 

IIRC, the thermal expansion problem was mostly an issue with BDD over titanium. Anyway, as of right now, you can buy solid CVD BDD anode material and apparently you can buy anodes of BDD over a substrate of niobium, tantalum or tungsten, here (I don't know what the price is but it's probably very expensive).

 

Anyway, in Henri Beer's US patent# 3864163, in addition to the "paint and bake" methods, he also describes the use of electrophoretic deposition (example 3) and mechanical attachment (example 11), both using preformed metal oxide powders.

 

I'm suggesting that BDD nanopowder might be able to be electrophoretically deposited or mechanically attached to platinum, glassy carbon or some other suitable surface.

 

 

 

No one is discussing what the actual cost of a useable electrode will be. So far, platinum or lead dioxide are looking MUCH more atractive (and available).

 

 

 

The way I see BDD powder being used - by us - is as an outer layer over platinum, lead dioxide or even an off-the-shelf MMO anode, for example. Platinum is expensive, but what if you could inexpensively apply some delta-Bi2O3 or BDD over it? Maybe it could be made to last almost indefinitely and also be made more efficient (for perchlorate production)?

 

 

 

As for Bi₂O₃ electrodes, has anyone put forth ANY evidence of their utility for perchlorate production? Theory is fine, but useless for practical application till proven.

 

 

 

AFAIK, no, there are no published papers that I'm aware of regarding the use of delta-Bi2O3 for perchlorate. Welcome to the "cutting edge". Until someone tries it, it will always be a theory, just like Henri Beer's ideas were until he tried them. I hope to try depositing delta-Bi2O3 over some platinum wire in the near future, but I have to wait until I have a place to work - which is always my problem.

 

 

 

The ability of individuals to access perc in the UK as well as the EU may well foreshadow a similar situation in the United States as well as other parts of the globe if political situations continue on their current apparent course. The only obvious solution is to produce it yourself to supply your research needs. Though this will avoid the "private sale" ban, the problem still exists if private posession is banned.

 

 

 

You can say that again...and again and again and again. The "political situation" if you can even call it that anymore, is completely out of control.