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making potassium (per) chlorate


gods knight

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Ebay seems to be the best place to buy Platinum bullions. I tried to buy them from precious metal trading sites (like Suisse Gold) and they had a minimum order of about 20,000 dollars... looks like they didn't like people buying a gram of Platinum a month to act as a regular savings but caters to people doing major investments.

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Bars are as here
The cathode is bent around the Pt bar. It is hard to see in both diagram and picture.
The bar measures 14.7mm x 8.9mm x 0.36mm giving a usable surface area of about 2.6 cm squared. If used at 400mA per square cm this gives a one amp anode. A lot smaller than I first guessed!
Platinum purchased this way (one gram bars) is approx. twice the price of spot. I thought it was cheaper.
We shall soldier on. The anode will last a very long time imo.

PAMPANODE

pamp 1

pamp 2

 

 

eb

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The photo doesn't show a clear gap between the anode and cathode (they look like they're touching).

 

Since I have spot welding equipment, that would be my preferred method of attachment, but I see nothing wrong with clamping the platinum anode to the lead as long as all the components (conductors and insulators) are compatible with the cell environment.

 

If I couldn't weld the Pt to Ti, my second choice would be to rivet the Pt with a fabricated CP titanium rivet. My circumstances are different from many amateurs as I have metal working capabilities and tools on hand. Between myself and my next door neighbor (an amateur jeweler and artist) we can do a lot with precious metals.

 

I was considering buying a Pt bullion piece and forming it into foil, then carefully spot welding it to a small CP titanium frame (to support it) with a power lead attached. I haven't done so because I've been able to purchase platinum plated titanium mesh anodes inexpensively on eBay.

 

That said, I cheer you on and look forward to your progress. Let us know how it goes.

 

WSM B)

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There's a lot of things involved in a chlorate cell that can turn the solution sort of yellow. Any iron that might be dissolved will probably appear slightly yellow as well. In any case, it's really only a problem if it's interfering with the cell, or makes it into the final product. Chlorate cells aren't going to be pretty.

 

Beauty is in the eye of the beholder; but still, it's a point well taken.

 

WSM B)

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Is this a sodium chlorate cell?

I find sodium chlorate cell liquor has a yellow-green color as it forms. Like bleach.

Potassium chlorate cells have this as well. I think hypochlorite just has that color.

 

I never bothered with ph control because I was just lazy and I ended up with more chlorate than I can use anyways (had to destroy them all when I moved to the US).

 

For all I've ever done and researched, I haven't yet applied pH control to one of my experimental cells.

 

I do have the materials and equipment, I wanted to solidly establish the uncontrolled cell parameters first, then add in pH control to clearly document the differences.

 

I fully expect that once I start to use pH control in chlorate cells, I won't go back to uncontrolled cells.

 

I'm also interested in making a highly purified product (better than commercial materials). That appears to be a worthy goal to me (why put all the effort in just to end up with a mediocre product ;)).

 

WSM B)

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I've seen these in gold, but they're also apparently available in platinum, which could possibly be adapted as anodes. After use, they could be redeemed at the local coin shop, not too much worse for the wear. I read somewhere that the platinum loss was only milligrams per 10kg of perchlorate produced. Maybe a quick polishing would restore the shine to this 50 gram piece of bullion? Just a rich thought.

http://www.apmex.com/product/75736/50x-1-gram-platinum-combibar-valcambi-in-assay

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I've seen these in gold, but they're also apparently available in platinum, which could possibly be adapted as anodes. After use, they could be redeemed at the local coin shop, not too much worse for the wear. I read somewhere that the platinum loss was only milligrams per 10kg of perchlorate produced. Maybe a quick polishing would restore the shine to this 50 gram piece of bullion? Just a rich thought.

http://www.apmex.com/product/75736/50x-1-gram-platinum-combibar-valcambi-in-assay

 

I like this item and wasn't aware of it's availability.

 

I wouldn't use it and try to later return it, though (that would be fraud).

 

If one were to invest in platinum for a perchlorate anode, it might be wise to invest in a "dissolved platinum" reclamation scheme, so any losses could be recovered.

 

WSM B)

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In an amateur cell, platinum losses may be high and that ingot will be sold weighed to probably 6 decimal places in grammes or troy measure. It will weigh light and probably be a different colour from a fresh ingot.

 

Platinum electrodes are available on ebay but have very small area, platinum sheet is available from ebay and other places 25mm x 25mm x 1mm thick might be good.

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Wow!

 

Platinum prices have really come down.

 

A few years ago when I looked (back when I was still in Taiwan and wanted to get a Pt bar for perchlorate manufacture), Pt bar was 90 dollars a gram.

 

What happened? Now it's around 40!

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Wow!

Platinum prices have really come down.

A few years ago when I looked (back when I was still in Taiwan and wanted to get a Pt bar for perchlorate manufacture), Pt bar was 90 dollars a gram.

What happened? Now it's around 40!

 

I've followed platinum prices for more than a decade now and it's varied from about $800 to $2000 per ounce (Troy = 31.1 g). At 50 grams the price is currently about $1500 for that 50 gram bar.

 

I think I'll stick to the platinized titanium mesh and lead dioxide on titanium anodes for my perchlorate production, for the time being.

 

WSM B)

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Hi Kevin, Let's see if I can answer these concerns.

 

The grey sediment on the bottom of the cell can be from the electrodes. Most people first suspect the anode is being attacked, but for some reason I find the cathodes are more likely the source of the sediment. I haven't figured why this is the case, but there are several possible causes (to be determined later).

 

I'll write more later about the other observations...

 

WSM B)

 

Edit, As far as the high concentration of HCl, water is consumed by the process so replacing it with more diluted acid is okay in my opinion.

The hypochlorite, et cetera, formed as the cell runs accounts for the faint yellow color (I've seen the same thing in my cells). The color clarifying is another matter. It's quite likely you've over-shot the desired levels by using higher concentrations of additives, tus changing the chemistry to where it's not making what we want.

 

Try diluting the acid to 8% or 10% (and go light with the amounts added) and see if you can more accurately track the changes. Good luck.

 

WSM B)

 

Hi WSM,

 

As far as the electrodes go I'd have to agree. My anode still looks almost perfect whereas my cathodes are definitely being affected. I've noticed some interesting splotchy yellow discoloration on the cathodes that didn't come off when washed with dish soap and water- I'll post a picture soon.

 

I missed reading your edit and came to the opposite conclusion that I may actually be adding too little. I've had my needle valve just about closed and the solenoid valve opening for just 5 seconds every twenty minutes and the pH still appeared too low so I started to wonder if maybe my pH was simply beyond the range of my papers.

 

My glass jar has also been etched from the solution, as I've been warned could happen. It was my understanding that this is exacerbated at higher temperatures and at a high pH. The etching seemed to become worse after my third run versus my second (The third being at a higher average temperature and received less acid). I'm currently running at 60C and would like to increase once I'm confident my pH is where it's supposed to be.

 

What kind of smell should the cell liquor have when proper pH control is implemented (or even if the pH is too low)? My two recent runs have had a near overpowering smell of what I believe to be hypochlorite; I'm thinking this is another symptom of high pH- unless there's a strong smell even at the magic 6.8.

 

Yeah it'd be nice to dilute the acid further- that way it's also not such a shock when it enters the cell.

 

I'm currently running my potassium chlorate cell a fourth time with a higher rate of acid doses- I'll report my findings once completed. Thanks for the help!

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Hi WSM,As far as the electrodes go I'd have to agree. My anode still looks almost perfect whereas my cathodes are definitely being affected. I've noticed some interesting splotchy yellow discoloration on the cathodes that didn't come off when washed with dish soap and water- I'll post a picture soon.

I missed reading your edit and came to the opposite conclusion that I may actually be adding too little. I've had my needle valve just about closed and the solenoid valve opening for just 5 seconds every twenty minutes and the pH still appeared too low so I started to wonder if maybe my pH was simply beyond the range of my papers.

My glass jar has also been etched from the solution, as I've been warned could happen. It was my understanding that this is exacerbated at higher temperatures and at a high pH. The etching seemed to become worse after my third run versus my second (The third being at a higher average temperature and received less acid). I'm currently running at 60C and would like to increase once I'm confident my pH is where it's supposed to be.

What kind of smell should the cell liquor have when proper pH control is implemented (or even if the pH is too low)? My two recent runs have had a near overpowering smell of what I believe to be hypochlorite; I'm thinking this is another symptom of high pH- unless there's a strong smell even at the magic 6.8.

Yeah it'd be nice to dilute the acid further- that way it's also not such a shock when it enters the cell.

I'm currently running my potassium chlorate cell a fourth time with a higher rate of acid doses- I'll report my findings once completed. Thanks for the help!

 

 

The yellow discoloration sounds like a titanium salt or compound (as does the dark residue in the bottom of your cell [i've seen it in some of my cells too]). Try soaking the cathode plates in straight hydrochloric acid and see if the discoloration disappears. Soaking the MMO anode doesn't hurt it, and it's one method of removing (acid soluble) contaminants.

 

By my understanding, the electrolyte at a pH no lower than 6.5 will smell like bleach (a hypochlorite, chlorite mix, actually).

 

When the cell runs too acidic (a pH of 6.0 and lower, I believe), chlorine gas will evolve, and it definitely has an overpowering smell.

 

Where and how you add the acid in a chlorate cell, can have a dramatic effect. Swede and others have seen this and commented on it in their posts. If your cell is running alkaline (naturally, without acid additions), and acid is dropped on top of the electrolyte surface it'll reward you with a puff of free chlorine gas (an unpleasant experience, to be sure).

 

Swede's simple but elegant solution was to inject (diffuse) the dilute acid in small doses, slowly and well under the surface of the electrolyte, so the chlorine evolved would remain in solution, where it contributes to the desired reaction, rather than flash off the surface and into the atmosphere, where it's wasted.

 

He installed a tube in the lid of his cell for acid additions, which ran to a point well below the liquid surface, and cross drilled the acid injector tube with many small holes near the bottom end so the acid could slowly diffuse into the electrolyte. A small diameter rigid PVC (or any compatible polymer) pipe or tube would work well.

 

I like this concept and I think it will work well for all of us. I would rather we use less acid than risk overdosing the cell. A basic rule is don't let your pH run too low (perhaps no lower than 6.2, for safety).

 

Hopefully this helps.

 

WSM B)

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The yellow discoloration sounds like a titanium salt or compound (as does the dark residue in the bottom of your cell [i've seen it in some of my cells too]). Try soaking the cathode plates in straight hydrochloric acid and see if the discoloration disappears. Soaking the MMO anode doesn't hurt it, and it's one method of removing (acid soluble) contaminants.

 

By my understanding, the electrolyte at a pH no lower than 6.5 will smell like bleach (a hypochlorite, chlorite mix, actually).

 

When the cell runs too acidic (a pH of 6.0 and lower, I believe), chlorine gas will evolve, and it definitely has an overpowering smell.

 

Where and how you add the acid in a chlorate cell, can have a dramatic effect. Swede and others have seen this and commented on it in their posts. If your cell is running alkaline (naturally, without acid additions), and acid is dropped on top of the electrolyte surface it'll reward you with a puff of free chlorine gas (an unpleasant experience, to be sure).

 

Swede's simple but elegant solution was to inject (diffuse) the dilute acid in small doses, slowly and well under the surface of the electrolyte, so the chlorine evolved would remain in solution, where it contributes to the desired reaction, rather than flash off the surface and into the atmosphere, where it's wasted.

 

He installed a tube in the lid of his cell for acid additions, which ran to a point well below the liquid surface, and cross drilled the acid injector tube with many small holes near the bottom end so the acid could slowly diffuse into the electrolyte. A small diameter rigid PVC (or any compatible polymer) pipe or tube would work well.

 

I like this concept and I think it will work well for all of us. I would rather we use less acid than risk overdosing the cell. A basic rule is don't let your pH run too low (perhaps no lower than 6.2, for safety).

 

Hopefully this helps.

 

WSM B)

Some kind of titanium compound makes sense. I gave my anode a hydrochloric acid soak last year after mounting it to the titanium tubing- turned the acid a yellow color from dissolved iron, I believe. Might have to give the cathodes a soak.

 

 

I have a tube in the shape of the letter J with several small holes in the end. I used this shape because when my initial run was completed, a few days after I stopped adding acid, I noticed that the fluid level inside the tubing was well above the holes, meaning acid was still seeping into the cell.

 

I do believe you are correct, WSM, that my acid dosing rate is too high. Less K-chlorate seems to be forming at the bottom than I'd expect at this point and, after increasing the acid rate yesterday, there may be even less present today. I should add that my cell temperature is maintained at 60C, within about 0.3C by means of an internal temperature sensor controlling an external fan, so I've ruled out temperature increase as the cause of my crystals' disappearance.

 

The thing that's confusing me the most, however, is the apparent lack of change of the pH. When dosing the acid- even at a very low rate- the pH seems to settle at around 6. If I cut the rate in half, it's the same and if I stop adding acid altogether it looks to be about the same- even after a few days.. I must be reading my pH papers wrong or maybe they aren't very good. I got them this past Winter from ebay. When I dip them in the solution, the bottom part of the paper is bleached pretty much instantly, so I look above, where it has soaked up the paper a little bit and compare its color to the colors on the pH paper packaging.

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Some kind of titanium compound makes sense. I gave my anode a hydrochloric acid soak last year after mounting it to the titanium tubing- turned the acid a yellow color from dissolved iron, I believe. Might have to give the cathodes a soak.

I have a tube in the shape of the letter J with several small holes in the end. I used this shape because when my initial run was completed, a few days after I stopped adding acid, I noticed that the fluid level inside the tubing was well above the holes, meaning acid was still seeping into the cell.

I do believe you are correct, WSM, that my acid dosing rate is too high. Less K-chlorate seems to be forming at the bottom than I'd expect at this point and, after increasing the acid rate yesterday, there may be even less present today. I should add that my cell temperature is maintained at 60C, within about 0.3C by means of an internal temperature sensor controlling an external fan, so I've ruled out temperature increase as the cause of my crystals' disappearance.

The thing that's confusing me the most, however, is the apparent lack of change of the pH. When dosing the acid- even at a very low rate- the pH seems to settle at around 6. If I cut the rate in half, it's the same and if I stop adding acid altogether it looks to be about the same- even after a few days.. I must be reading my pH papers wrong or maybe they aren't very good. I got them this past Winter from ebay. When I dip them in the solution, the bottom part of the paper is bleached pretty much instantly, so I look above, where it has soaked up the paper a little bit and compare its color to the colors on the pH paper packaging.

 

Do you have a way to determine the chloride level?

 

I ask because one possible reason for the K-chlorate formation to slow down is that the chloride level usually drops continually as the chlorate forms. Unless you replenish the chloride levels as the chlorate forms, the progress of the run would be self-limiting.

 

Do you think this might be what you're seeing?

 

WSM B)

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I suppose I could check the density, but based on the time elapsed and when comparing the voltages, current, temperature and crystal depth to my previous two runs, I'm inclined to say this shouldn't be the case. The possible exception (that I can think of) being that chloride ions have been oxidizing to chlorine gas and exiting the cell due to the pH being too low. I'm very sure I overdosed my cell last night as I increased the acid rate considerably and by this morning the electrolyte was up to the bottom of my lid and bubbling into my vent tube. On the plus side, I now know everything is sealed very well as there were no leaks! However, if a large portion of the chloride had gassed off, shouldn't that also decrease the cell's conductivity? I ask this because the voltage across my electrodes started around 4v - 4.1v and last run I stopped it at around 4.9v - 5v (don't have my notebook at the moment) but it's currently only at around 4.2v, with a constant current of around 20.4 amps.

 

edit: A while ago I made a note of something Swede had posted about the rate of acid dosing. Adding 0.057 mL of 32% HCl per amp per hour with the HCl volume cut by 33% after crystals form seemed to be the ideal rate for him. Is this a good rule of thumb to go by? It's those numbers that also led to my believing that I wasn't adding enough HCl to my chlorate cell. I'm also wondering now, how susceptible is this rate to the cell temperature?

 

Here's a picture of the previously mentioned yellow discoloration of my cathodes:

20170812 011622

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A while ago I made a note of something Swede had posted about the rate of acid dosing. Adding 0.057 mL of 32% HCl per amp per hour with the HCl volume cut by 33% after crystals form seemed to be the ideal rate for him. Is this a good rule of thumb to go by? It's those numbers that also led to my believing that I wasn't adding enough HCl to my chlorate cell. I'm also wondering now, how susceptible is this rate to the cell temperature?

 

I believe it is, and a good starting point. Remember, if you dilute the acid, increase the volume by that same amount.

 

If you drop the acid to an 8% solution (1/4 of full concentration), multiply the volume by 4 and see if that works for you.

 

WSM B)

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In the HOT chlorate cell process the acid is added to the chloride solution added to keep the volume constant, by dip tube to the bottom of the cell.

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Okay I will put one on order when I get paid and we will see where I am at when it is connected...

Thanks again WSM

hey guys.. after a little Break I'm back with an other run of a quick and dirty 10l Cell@125A.

Pictures will come thursday or friday when everything is finished :)

 

Since my last visit many things where written here, so i give them a read in the next time.

 

now, to give you some help with your current-meter if its not too late:

The Values for the shunt and the decimal place are normally set by jumpers and/or Potentiometers beneath the cover of the front, so you might take a look.

 

 

greetings, PTFE

 

edit1

 

Did you get any salt creep coming through in between the boro. glass and the PTFE tubing?

 

 

Hey kevin. Sorry for my late response.

I never had any salt creep around the tube.

Also you have to fill the tube up with water, to get a better Heat conductivity, this will stop any electrolyte or Salt crystals from entering your sensortube.

Edited by PTFE
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Some kind of titanium compound makes sense. I gave my anode a hydrochloric acid soak last year after mounting it to the titanium tubing- turned the acid a yellow color from dissolved iron, I believe. Might have to give the cathodes a soak.

I have a tube in the shape of the letter J with several small holes in the end. I used this shape because when my initial run was completed, a few days after I stopped adding acid, I noticed that the fluid level inside the tubing was well above the holes, meaning acid was still seeping into the cell.

I do believe you are correct, WSM, that my acid dosing rate is too high. Less K-chlorate seems to be forming at the bottom than I'd expect at this point and, after increasing the acid rate yesterday, there may be even less present today. I should add that my cell temperature is maintained at 60C, within about 0.3C by means of an internal temperature sensor controlling an external fan, so I've ruled out temperature increase as the cause of my crystals' disappearance.

The thing that's confusing me the most, however, is the apparent lack of change of the pH. When dosing the acid- even at a very low rate- the pH seems to settle at around 6. If I cut the rate in half, it's the same and if I stop adding acid altogether it looks to be about the same- even after a few days.. I must be reading my pH papers wrong or maybe they aren't very good. I got them this past Winter from ebay. When I dip them in the solution, the bottom part of the paper is bleached pretty much instantly, so I look above, where it has soaked up the paper a little bit and compare its color to the colors on the pH paper packaging.

 

Those who use pH control (HCl acid injections to lower the alkalinity) have reported that the amount of acid required diminishes as the cell runs. The pH tends to reach something of an equilibrium where further acid doses either aren't needed or the amount is greatly reduced.

 

Swede said something about dropping the acid injections to 2/3 the starting amounts when KClO3 crystals start to form. Since everyone's cell is different, I would suggest we use his recommendations as a starting point only, and fine tune our cell from there. Realize that the chlor-alkali cell is a complex and dynamic environment, with all the components in a state of constant flux.

 

This is what we want; we take a stable salt solution, add current and drive the reaction to build desired compounds. Lots of changes happen in the solution as we do so, all at the same time, and the complexity of it is the subject of Doctoral dissertations. The exact chemistry of what is in our cells at any given moment is highly dependent upon where in the process we are and for how long it has run (plus myriad other variables).

 

Optimizing our cell for the highest efficiency is tricky business, and adding acid with a light hand plus careful monitoring is called for. Even then, the cell's requirements change as it goes, so no hard, fast rules will do the job, but we need to watch it carefully and respond appropriately according to the changes we observe.

 

All this is not easy, but it is worth it; especially if you are scaling up the scope of your operation.

 

WSM B)

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Those who use pH control (HCl acid injections to lower the alkalinity) have reported that the amount of acid required diminishes as the cell runs. The pH tends to reach something of an equilibrium where further acid doses either aren't needed or the amount is greatly reduced.

 

Swede said something about dropping the acid injections to 2/3 the starting amounts when KClO3 crystals start to form. Since everyone's cell is different, I would suggest we use his recommendations as a starting point only, and fine tune our cell from there. Realize that the chlor-alkali cell is a complex and dynamic environment, with all the components in a state of constant flux.

 

This is what we want; we take a stable salt solution, add current and drive the reaction to build desired compounds. Lots of changes happen in the solution as we do so, all at the same time, and the complexity of it is the subject of Doctoral dissertations. The exact chemistry of what is in our cells at any given moment is highly dependent upon where in the process we are and for how long it has run (plus myriad other variables).

 

Optimizing our cell for the highest efficiency is tricky business, and adding acid with a light hand with careful monitoring is called for. Even then, the cell's requirements change as it goes, so no hard, fast rules will do the job, but we need to watch it carefully and respond appropriately according to the changes we observe.

 

All this is not easy, but it is worth it; especially if you are scaling up the scope of your operation.

 

WSM B)

 

I think this is the explanation I've been looking for to solve the mystery as to why my pH doesn't seem to increase. In my last few trials I've added too much HCl and brought the pH too low, leading me to stop all acid additions in efforts to increase it. However, even after several days my pH barely gets about 6.

 

I diluted my HCl to 10% for my latest K-chlorate run but it appears my pH is too low once again. It's tricky to get it just right! I didn't get the acid additions started until about a day and a half after the run began.I believe this resulted in an even greater acid demand initially, which would likely have decreased very rapidly upon reaching 6.7- 6.8.

 

I'm also running into a new problem now: It seems that after beginning to regulate my cell's temperature, the crystals at the bottom form a nearly solid mass. After my last run, I had to break the chlorate crystals into a couple large pieces with a plastic rod and a hammer to be able to remove them. Any suggestions as to how to avoid this? I'm thinking of insulating the lower portion of my cell to see if it helps any.

 

With regards to my earlier comments about the cell electrolyte' smell: after some research I found that hypochlorite decomposes naturally to produce primarily salt and oxygen. However, when the pH is acidic, chlorine gas is also formed, which would explain the smell- and its persistence- of my electrolyte.

 

 

In the HOT chlorate cell process the acid is added to the chloride solution added to keep the volume constant, by dip tube to the bottom of the cell.

 

This is the ideal I'm hoping for- once I get my cell figured out. That said, I'm hoping to scale up and switch to sodium chlorate in the future for the purpose of making potassium perc, which means a whole new system to figure out- I think I opened Pandora's box when I got into this!

 

Thanks again for all the help,

 

Kevin

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I think I opened Pandora's box when I got into this!

 

I SO understand, and yet; isn't it a fascinating journey?!!

 

The further I get into this pursuit, the more I learn and am able to do. Many interesting insights and a lot of understanding has come my way during this process. The problem is, no one lives long enough to make all the mistakes themselves; therefore THANKS to all who've shared their electrochemical trials and experiences, with the group.

 

WSM B)

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A couple days ago I was shopping at a home furnishings store with my Wife and found a treasure. They were having a sale and clearing out last year's display models at incredibly low prices, so I picked up a huge glass vase that resembles a battery jar from the old days:

 

post-9734-0-54861000-1504362998_thumb.jpg post-9734-0-33545600-1504363026_thumb.jpg

 

This thing has a capacity of about 25 liters and is 58 cm tall (inside), has an inside diameter of 23.5 cm and the wall thickness is 7 mm.

 

Imagine what I think I can use it for?!! :lol:

 

If it works, wonderful; and if it doesn't, I'm only out $10 (plus the time invested in the project).

 

If you're living right (and keep your eyes open) things seem to work out.

 

WSM B)

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  • 4 weeks later...

attachicon.gifElectrolysis.JPG

 

New cell is in construction :)

Excellent! Can you share any details?

 

WSM B)

 

Edit: That's odd. I didn't see the drawing till I posted my uninformed response. That's the downside of using the "smartphone" to view posts on APC (darned tiny screen :( )

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I've decided to write the next part (Part 17) of the series, Homegrown Oxidizers, on the purification of raw materials as well as all the materials involved in every aspect of the process of creating our own oxidizers.

I plan to get back to the high temperature sodium chlorate experiment later, but for now it's on hold due to my very busy work schedule and home life.

I've got much more to share about purity and purification of the materials we use in preparing our pyrotechnic chemicals.

To be continued...

WSM B)

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