Making perchlorate

[Bonny]

If you already have sodium perchlorate and are trying to make potassium perchlorate, converting to acid is pointless. Simply adding KCl to the solution will convert it for you.

[pdfbq]

I dont think Frank is talking about KClO4 here.

 

I made some HClO4 this way but it is not that easy, at least not for me unfortunately. I used 30% HCl and had to boil it down and add fresh HCl three times iirc before I used all the NaClO4.

 

It would be a great way to make ammonium perc and I think in industry it is done this way but I found it too cumbersome. Also really hot fuming HClO4 scared me a bit.

Edited September 28, 2012 by pdfbq

[taiwanluthiers]

So why not add ammonium chloride to the sodium perchlorate? is it due to concerns of residual chlorates?

 

I really don't think I want to be making Perchloric acid... I can actually buy the stuff (its expensive) and I won't even buy it. I generally avoid buying any strong acid in fact...

 

Also in case you don't know, always add acid to water, not the other way around. Strong acids tend to produce heat when diluted and when adding water to acid, the heat can cause the water to boil (like adding water to hot oil) and cause the acid to splatter.

Edited September 28, 2012 by taiwanluthiers

[pdfbq]

Because then you have to seperate the aperc from the NaCl. If you make it from HClO4 you end up with aperc only.

 

[taiwanluthiers]

You have to do the same with potassium perchlorate, you dissolve the crystals in boiling water until saturated, then cool to 0 degrees and filter out the crystals. Sodium chloride is highly soluble so will wash out and you don't lose that much ammonium perchlorate. Its much easier with potassium perchlorate though because it is almost insoluble in water.

[pdfbq]

Its much easier with potassium perchlorate though.

Exactly.

 

Edit: aperc is still soluable at 0. To get rid of all your NaCl you have to rekristallize another 2 times which means a total aperc loss of iirc 40-50%.

 

one way to deal with that is after all add KCl to your rest-solution to convert the leftover aper to kperc.

 

The HClO4 route should/could be a very good route but I had trouble making the acid and I also do not know if the conc. acid is Cl- free.

Edited September 29, 2012 by pdfbq

[taiwanluthiers]

Has anyone successfully made perchlorate with MMO anode and Ti cathode?

[WSM]

Has anyone successfully made perchlorate with MMO anode and Ti cathode?

 

I've been interested in chlorate and perchlorate chemistry for about ten years, and as far as I know, no, no one has. At least not with the MMO used for the chlor-alkali, saltwater pool or cathodic protection industries.

 

WSM

Edited October 3, 2012 by WSM

[WSM]

So why not add ammonium chloride to the sodium perchlorate? is it due to concerns of residual chlorates?

I really don't think I want to be making Perchloric acid... I can actually buy the stuff (its expensive) and I won't even buy it. I generally avoid buying any strong acid in fact...

Also in case you don't know, always add acid to water, not the other way around. Strong acids tend to produce heat when diluted and when adding water to acid, the heat can cause the water to boil (like adding water to hot oil) and cause the acid to splatter.

 

I imagine if you neutralize any chlorate in the sodium perchlorate solution before adding the ammonium chloride, the need to make perchloric acid is overcome. Industry typically makes ammonium perchlorate from sodium perchlorate, without the perchloric acid step. We should be able to also.

 

Personally, for pyrotechnics I find potassium perchlorate and potassium chlorate so much more useful than the ammonium salt, I fail to see the need for it (unless your goal is polymer bound rocket propellants). I've used both perchlorates and prefer the potassium salt.

 

WSM

[WSM]

I dont think Frank is talking about KClO4 here.

I made some HClO4 this way but it is not that easy, at least not for me unfortunately. I used 30% HCl and had to boil it down and add fresh HCl three times iirc before I used all the NaClO4.

It would be a great way to make ammonium perc and I think in industry it is done this way but I found it too cumbersome. Also really hot fuming HClO4 scared me a bit.

 

If one is determined to make perchloric acid, the best method I can suggest is in borosilicate ground glass distillation equipment, using a perchlorate salt in concentrated sulfuric acid and an electric heating mantle with a variac power source. Follow all proper laboratory proceedures and be safe. I also recommend using Teflon thimbles on the ground glass joints so they don't get stuck together permanently.

 

Be sure to wear all the proper PPE's, too.

 

WSM

[WSM]

Look for KCl as water-softener substitute. A 40 pound bag costs less than 50 cents a pound, and it is more than adequate for this process.

Reagent-grade stuff is cost=prohibitive, and agricultural KCl is going to have more impurities than the water-softener grade.

 

Quite true, and if you want purer KCl, try dissolving the water softener grade, filtering any debris out and recrystallizing it for a better grade of starting material. It takes more time than using the salt right out of the bag, but if a pure product is your goal, then why not?

 

Then again, you can do this with the agricultural grade too!

 

 

WSM

[pyrojig]

I have found what these fellows are saying to be true. When chlorate crystallizes out of solution , it is natures way of purifying a salt. With the proper wash after extraction, you have a great pyro grade kclo3.

 

I have made amazing blue stars out of my kclo3 prepared in this manner. I believe that it was Swede that mentioned the kclo3 he tested in this manner was close to the 99% purity.

If there is no need to have reagent lab grade kclo3 , then simplicity is your friend. A process that required the least amount of labor, and using store bought water softener, will give your the most for your buck. Heck why go the extra mile if all your after is pyor grade kclo3?

[Swede]

^^ And that's it in a nutshell! pyrotechnics grade KClO3 is a snap with MMO these days, and since we are not NASA or a research lab in need of 99.999% pure KClO3, what comes out of a cell, given a good wash with cold water, is going to be more than adequate for pyro use.

 

I'm happy to hear that your blue stars came out so nice. What formula did you use?

[pyrojig]

Im not sure exactly,( I have been trying many diff formulations) but I know it utilized the copper oxychloride , and they where a nice crisp blue. I have to say, chlorate stars are nice for their large flame and ease of ignition. Paris green is the main focus for the the blue Im after. I dig some of those "old school " formulations( the good ones that is) .

[WSM]

Im not sure exactly,( I have been trying many diff formulations) but I know it utilized the copper oxychloride , and they where a nice crisp blue. I have to say, chlorate stars are nice for their large flame and ease of ignition. Paris green is the main focus for the the blue Im after. I dig some of those "old school " formulations( the good ones that is) .

 

Yup! Me too. I remember, long ago, trying several blue formulations (making stars with them) and being unimpressed with them...UNTIL I put a few chlorate red and (Paris green) blue stars in the header of a 4 oz rocket. Oh WOW, what a beautiful color combination, and deep colors, too!

 

My problem was, I tested the stars by burning them on the ground or a nearby place. The blues always seemed pale and washed out, even the much touted Paris green blues. When they were further away, in the sky, I could finally appreciate their true beauty and depth of color.

 

The lesson I took from that experience is to not judge the colors or their saturation or hue till they can be seen at a distance and in the night sky. Even blues that appear to have a gold or reddish corona when burned nearby on the ground, may well look much better further away in the sky!

 

WSM

[taiwanluthiers]

By the way just an update to my (per)chlorate making situation.. (for anyone still following the thread)

 

I dissolved the red KCl, filtered the red crap off (very chalk like, no idea why they add it), and ran it in a MMO/Ti cell for a week, after which I get a bunch of crystals at the bottom of the cell. After crystalizing them once I made some blues with them. The blues are great but my only gripe with them is they burn really fast. I really wish there are ways to slow down the burn rate of KClO3 stars, perhaps red gum is the ticket. I thought about making Buell red with them (I prefer metallic red stars, better brightness and color), but I felt the chlorate made the formula burn with a lot of residue... in fact it wasn't red at all. Maybe I really have to go with Lancaster 1 red with chlorates, but again they burn way too fast.

[pyrojig]

That is a good prob to have for the most part. As in most shells it is best to obtain about a 2 sec burn time. This gives very clean looking breaks for warimono shells. This also allows the maker to roll larger stars, and get larger effects in the sky. Remember adding metals to star comps makes them burn faster.

 

Might try this comp( Japanese ) for a tad slower blue. It is best rolled( but I did press the other 1/2 of the comp with great results):

65 kclo3

7 black copper oxide.

10 red gum

13 parlon

5 dextrin

[taiwanluthiers]

I have found red gum tends to burn slower than lactose...

[jholdswo]

I have read through all the stuff (original post years ago geocities, recently swede's blog etc.) and the quality of documentation of most certainly maturing. Don't burn me if this has been asked I don't "do th forum thing" often but I need to know about the Ti lugs on mmy PT anodes.

 

I had some very nice (and pricey, ouch) 2x6 in anodes built by Anomet from Pt Clad Ni wire with a copper core, 100 microinches of Pt. The woven wire anode actually exposes a lot less substrate than the old expanded mesh anodes. My Cathode is expanded mesh Ti of the same surface area as my anode. Cell is a 3L reaction flask and power is supplied by a 5V power supply capable of pushing 10 - 40 AMPS.

 

When my anode is down in the sol'n where the Ti lug extends partly into the bath. First, is that an issue? Second I am ultra paranoid about chlorate contamination having had a close call with an ill advised mixture calling for both Chlorate and Sulfur once. I have no intentions of combining anything acidic with chlorate so I have been trying to get my hands on N-Phenylanthranilic Acid to test for kclo3 but am having a real pain of a time tracking it down..... Carmine indigo seems a reasonable alternative and a more sensitive test so why does the collecrtive community seem so bunged to use the NPAA?

 

Lastly (I promise) did we ever get to the bottom of the efficay issue surrounding sulfite with the indigo carmine test. Did the Proof of Conept ever determine that Chlorate destruction using the Metabisulfate left residual traces to make the addition of sulfite unecessary for a conclusive test? And yeah.... I have access to lots of cheap perc but what fun is that??

[pdfbq]

@jholdswo

I do it the Indigo Carmine way without the sulphite. In my opinion it works like a charm.

I tested it by adding more than once, a micro part of KClO3 to a negative on ClO3^- tested sample of KClO4.

It immediately turned from blue to pale yellow.

[WSM]

I have read through all the stuff (original post years ago geocities, recently swede's blog etc.) and the quality of documentation of most certainly maturing. Don't burn me if this has been asked I don't "do th forum thing" often but I need to know about the Ti lugs on mmy PT anodes.

I had some very nice (and pricey, ouch) 2x6 in anodes built by Anomet from Pt Clad Ni wire with a copper core, 100 microinches of Pt. The woven wire anode actually exposes a lot less substrate than the old expanded mesh anodes. My Cathode is expanded mesh Ti of the same surface area as my anode. Cell is a 3L reaction flask and power is supplied by a 5V power supply capable of pushing 10 - 40 AMPS.

When my anode is down in the sol'n where the Ti lug extends partly into the bath. First, is that an issue? Second I am ultra paranoid about chlorate contamination having had a close call with an ill advised mixture calling for both Chlorate and Sulfur once. I have no intentions of combining anything acidic with chlorate so I have been trying to get my hands on N-Phenylanthranilic Acid to test for kclo3 but am having a real pain of a time tracking it down..... Carmine indigo seems a reasonable alternative and a more sensitive test so why does the collecrtive community seem so bunged to use the NPAA?

Lastly (I promise) did we ever get to the bottom of the efficay issue surrounding sulfite with the indigo carmine test. Did the Proof of Conept ever determine that Chlorate destruction using the Metabisulfate left residual traces to make the addition of sulfite unecessary for a conclusive test? And yeah.... I have access to lots of cheap perc but what fun is that??

 

I'll try to answer these questions in order:

• Titanium will handle the cell environment just fine as long as the power is applied (when the power is off, remove the electrodes from the cell). If you're concerned, wrap Teflon tape around the "Ti lug"
  
• Swede introduced the n-Phenylanthranilic acid test to us here and has been promoting it. I have used aniline HCl, NPAA and indigo carmine reagents to test for chlorate ions. They all work. The most sensitive in my estimation is the indigo carmine test
  
• I've tried the indigo carmine test with and without the sulfite. I believe it works better with the sulfite (and it works fine without heating; it just takes a bit longer)
  
• I haven't tried this but it makes sense that it would work and the indigo carmine reagent should work without adding additional sulfite if the metabisulfite were used in slight excess
  

These are good questions and well thought out.

 

Unfortunately, none of the test reagents are stable when made up and should be mixed fresh in small quantities when needed, to avoid being wasteful.

 

I suggest, since platinum doesn't fair well in a cell with chlorides, make your chlorate feed stock from chlorides with MMO anodes and use your platinum anodes for converting the purified chlorate solution to perchlorate. I believe the platinum anodes will last longer, especially if you keep the chlorate levels up.

 

WSM

Edited February 13, 2013 by WSM

[jholdswo]

Wow, that was a total "duh" moment. What an elegant solution and so simple to use the the MMO's in my double decomp from NACL to KCLO4 adventure. Thanks!!

 

Also, an apology to the group in general I have been updating two similar threads and I will be updating the "how to make (per)chlorate" thread going forward as not to confuse the issue,

 

Thanks again and this will not be a set back and only require a minimal rewrite of my test procedures and process but will be awesome as I was very concerned about Chlorides, temp and pH and the effects on my poor little 100 microinch clad Anodes.

 

And lastly I love this group because no one has even questioned my sanity for why I am doing this when perc is relatively easy to get and cheap in the US. When the zombies come skylighter, firefox, thunder valley etc. will be cut off as the infrastructure collapses (hope everyoone knows that is a retalitory mocking to my friends who questoin the efficacy of how I spend my leisure time).

[WSM]

Wow, that was a total "duh" moment. What an elegant solution and so simple to use the the MMO's in my double decomp from NACL to KCLO4 adventure. Thanks!!

Also, an apology to the group in general I have been updating two similar threads and I will be updating the "how to make (per)chlorate" thread going forward as not to confuse the issue,

Thanks again and this will not be a set back and only require a minimal rewrite of my test procedures and process but will be awesome as I was very concerned about Chlorides, temp and pH and the effects on my poor little 100 microinch clad Anodes.

And lastly I love this group because no one has even questioned my sanity for why I am doing this when perc is relatively easy to get and cheap in the US. When the zombies come skylighter, firefox, thunder valley etc. will be cut off as the infrastructure collapses (hope everyoone knows that is a retalitory mocking to my friends who questoin the efficacy of how I spend my leisure time).

 

Crazy is relative. When you associate with a bunch of inquisitive, science minded folks; peculiar is the rule and not the exception!

 

I've studied the subject of perchlorate production casually for a long time now, and I've come to the conclusion that the easiest or simplest way of making it is in two steps:

1. Convert chlorides to chlorates and purify them
   
2. Convert the purified chlorates to perchlorates, purify them and convert them to the various desired end products (KClO₄, NH₄ClO₄)
   

Is it easy? No.

Is it possible? Yes.

Is it worth it? It depends on your values. Knowing how to do it is of great worth to me; so yes, it is.

 

WSM