How to purify Barium Chlorate

[cmjlab]

I recently purchased some Barium Chlorate to try out some of the organic green formulas. To my disappointment, every composition I tried turned out very pale green(ish) and clearly contaminated by the sodium yellow flame.

 

In order to ensure it was the Barium Chlorate, I tried the following formulas.

 

1. I tried Hardt's Green #1 (uses Barium Chlorate, KCL03, and Barium Nitrate. RESULT: Crappy pale sodium yellow tinted, very pale green.

 

2. Tried Barium Chlorate (90%) / Shellac 10% (should make an excellent green by all accounts). RESULT: Same pale greenish, with obvious sodium yellow contamination.

 

Unless someone knows another test, I am hoping that I can purify the Barium Chlorate somehow to get at least some useable amount out of it. Based on the coloring of the flame it produces, I'd guess it's either Sodium Chlorate or Sodium and Calcium Chlorate.

 

Anyone have any ideas? Thanks.

 

Charles

[cmjlab]

I'm thinking I should be able to dissolve it in Boiling water, filter, then throw in freezer to crash the Barium Chlorate out, but not completely freeze (in order to keep at least some of the sodium available in the liquid to can't off - hopefully taking some of the sodium with it). Whatever crystals are left can be filtered off the rest of the remaining liquid, then rinsed with ice water (again hoping to not dissolve much of the Barium) and removing some more of the sodium contamination.

 

My hope is not that I will obtain "pure" Barium Chlorate, but to get rid of SOME of the sodium contamination, or enough to make a better green.

 

Someone on FW.com suggested separation of the Barium and Chloric Acid via flouric acid (or something similar - but I think Sulfuric would technically work) to convert Barium to Barium Sulfate (via precipitation and removal) which theoretically leaves Chloric Acid. This then gets treated with pure Barium Carbonate to re-make Barium Chlorate.

 

I see an issue with my lack of knowledge on how to ensure the solution of distilled water and Barium Chlorate is/stays dilute enough (min below 30%) to avoid stability issues with Chloric Acid. I also remember that concentrated sulfuric Acid acts like a dessicant to remove water during the nitrocellulose nitration reaction (nitric acid to nitrate / H2S02 to remove water during the process) - so I'd imagine that would be less than helpful if the goal is to ensure the chlorate remains dilute.

 

Even if I could make it to the point where I had a 30% solution of pure Chloric Acid in distilled water, I also see ensuring that my Barium Carbonate is actually pure as an issue too, though it makes a pretty good green.

 

Long story short - guess I'll stick with the water / recrystallization method for now, and see how that turns out. Sure hate to be out a bunch of Barium Chlorate.

 

Charles

[Richtee]

I’m in awe of the measures needed. Damn.

[mabuse00]

Im in awe of the measures needed. Damn.

 

Me too. I wonder if a barium chlorate cell is a better option.

Or, if possible, buy better stuff from a reputable dealer.

Edited October 22, 2022 by mabuse00

[Arthur]

It's mainly a cost vs effort vs value exercise. How much do you start with, how much will you end up with and how much will it cost you.

 

Is there a better supply of barium chlorate near you. Most times it's best to avoid fluorine acids for toxicity.

[Arthur]

 

even he says that this process is hard on the electrodes.

[cmjlab]

That is an interesting video. So he's using Barium Carbonate and Hydrochloric Acid to create a solution of Barium Hydrochloride (funny enough, its the color producing chemical contributed by the Barium Chlorate during thermal decomposition) - but because it's too hygroscopic to use by itself in a formula, he then goes onto synthesize the Barium Chlorate via electrolysis (which may or may not result in Barium Chlorate / Chlorite / or other potential bi-product(s), contingent on the pH management and chemicals used to reduce pH.... ) Lotta work / chemistry, I'd rather just use the carbonate or make sulfate and try with KCLO4 in a green composition.

 

Charles

[cmjlab]

Arthur,

 

In my case I already spent the money on Barium Chlorate but as mentioned earlier it's definitely contaminated. If I were a "bulk" consumer and bought a drum or more, I'd be in a position to demand the chemical purity I paid for. But since purchase was pounds, which came from the guy who DID buy the drum, I'd only get more of the same contaminated product even if he did send more.

 

Normally, I'd rather not mess with Chloric Acid and it's stability issues, not to mention I'm no chemist and can't do "stoichiometry" either. Plus I agree, it's a lot of work!

 

But, the more I think about it, the safest way for me to purify it "enough" to "improve" the color (I'm not looking for 100% purity) - is to exploit the solubility difference of Sodium vs. Varium Chlorate(s), and accept the inevitable loss of some (but no worse than 40% total loss).

 

I could also save the filterant/solution to try and salvage some .ore contaminated Barium Chlorate, but I really only want to make a small batch of Barium Chlorate green stars / products (~5-10 lbs +/-2 or 3 lbs).

 

I was hoping someone like Mumbles might weigh in with his chemistry background, but I'm guessing he's been busy lately.

 

Charles

[cmjlab]

Reading the science madness or Wikipedia information on Sodium and Barium Chlorate(s), I wonder if ethanol would work better to improve my yield, or if some mixture of alcohol and water.

 

It says that NaCLO3 is somewhat solubility in ethanol, but BaCLO3 is not measurably soluble in ethanol.

 

If I used a mixture of 75/25 ethanol/water would that further limit the Bariums soluability and total loss %?

[Arthur]

Reading the science madness or Wikipedia information on Sodium and Barium Chlorate(s), .

 

It says that NaCLO3 is somewhat solubility in ethanol, but BaCLO3 is not measurably soluble in ethanol.

 

 

 

Science madness isn't my favourite information source, BUT, If that info is correct then repeated washings with small portions of ethanol (which could be recovered by distillation (Carefully there's a fuel and an oxidiser) should remove the sodium salt and let the barium salt remain without impurities. My first move would be to fill a buchner funnel with raw chlorate and wash repeatedly with ethanol under vacuum. Likely an accumulation of sodium salts in the alcohol would eventually make a yellow flame test.

 

BE EXTREMELY CAREFUL alcohol flames and chlorates seems like a hazardous environment.

[Powderman]

I would try washing small sample of the Ba(ClO3)2 with ethanol, dry it and test it. If it works scale up.

Recrystallization is common practice and difference in solubility of Ba and Na chlorates are in Your favor. Try it if ethanol fails.

Acid will not help with the Na problem, it will stay in solution with HClO3.

[justvisiting]

I bought some barium chlorate way back when that is as described by the OP. It's funny how the bad chems that show up here and there don't disappear, they just re-appear years later somewhere else I thought I was onto something by re-crystallizing, and I was- sort of. I made a supersaturated solution and hung a string in it to let the crystals grow on after it cooled. The barium chlorate that crystallized on the string made a perfect green. The details are hazy now but the rest of the stuff was still contaminated. I'm guessing that repeated dissolving and partial re-crystallization would yield quite pure chlorate at the beginning of the crystallization each time, with the contaminants building up in the rest of it. I poured off a bunch of the saturated liquid and used it to make barium sulfate for strobe rockets and it worked well. Rinsing the sulfate with copious amounts of clean water washed away the (presumably) calcium and sodium sulfates. The sulfate was quite resistant to drying for some strange reason. I talked about it on FW. Maybe the details were better explained on there. Haven't been there in a bit.

[cmjlab]

JustVisiting - Thanks for the info. I'll search on FW.com in a bit. Mr. Swisher did provide some theoretical processes that could take me to a better product, but they involved a longer process than the Sulfuric Acid route - perhaps it was a safer way that ensures the Chloric Acid stays dilute below 30% (where with Sulfuric Acid I've no idea how much water is required in proportion to Sulfuric Acid to prevent an unwanted reaction.

 

With your string did you need to start it with a seed crystal? Or did it form there on its own without any input?

 

If you already covered that over on FW.com you can disregard, I'll find it there so you don't have to repeat yourself! Thanks again.

 

Charles

[cmjlab]

JustVisiting - I found your post on FW.com, I have to admit I was surprised at the easy method of "double displacement" I never thought would work. A simple solution of Magnesium Sulfate with the Barium Chlorate (if I understood correctly). I didn't think you'd be able to go directly from Chlorate to Sulfate using that route, I would have thought it'd require Barium Carbonate or better yet, Barium Chloride in solution.

 

Charles

[pyrokid]

Could you please share the source of the problematic material? I am surprised you can not get a refund. Barium chlorate from a pyro supplier should be free from sodium contamination.

[Crazy Swede]

The suggestion in FW was to dissolve the contaminated barium chlorate in Hexafluorosilicic acid but that is NOT for the inexperienced!

 

Glassware cannot be used and there is a risk of exposure to deadly HF gasses!

[Arthur]

When there is a method using alcohol (likely available from Ace Hardware) why look to rarer chemicals with extreme handling and safety reservations.

[cmjlab]

If I don't get a response I will certainly share so others may avoid similar issues. I'm still waiting though, I emailed mid to late last week, and will try again tomorrow (normal buss hours). If still no response, then I'm under no obligation to be concerned about "harming business".

 

Suede / Arthur - I agree, I've settled on ethanol rinse first, if no improvement, then water recrystallization (as I'm convinced it's a sodium not calcium impurity), then if all else fails, Sulfuric Acid to sulfate (using excess of distilled water), and Barium Carbonate to neutralize remaining acid to see what the end product results in (Barium Chlorate or some mixture of sulfate / chlorate).

[Powderman]

Sulfuric acid will isolate Ba from Na, but you can´t separate chloric acid from Na contamination this way - both stay in solution. After reaction with Ba carbonate the resulting solution will contain the same amount of Na as before. And I would be very careful to mix sulfuric acid with impure chlorate - if it contains chlorides, chlorine gas will be produced and that is not a good thing in any way.

[Arthur]

We already have a method based on the fact that the sodium salt is slightly soluble in alcohol but the Barium salt is not. Wash the mix with alcohol, filter and dry it. Retest for improved flame colour purity. Much alcohol may be needed bit with care it can be redistilled as needed.

[cmjlab]

An update on the ethanol.

 

I took 500 grams of Barium Chlorate and rinsed it in Ethanol. (Put the Barium Chlorate in a bowl, poured in twice as much that covered the individual grains, and stirred for around 5 minutes. Then drained into a filter poured in more clean alcohol.)

 

Out of curiosity, I kept some of the ethanol from the initial rinse to see if any sodium or Barium was in suspension. I lit the small amount of ethanol in a tin foil cup, expecting to see some yellow flame or even a grain of Barium burn green. It did NOT burn color, except clean blue of plain ethanol.

 

So I boiled some clean ethanol (double boiler) and tried again, same method / process. Tried a burn test again, same results - clean blue flame.

 

Moral of the story, if there is contamination, the Barium needs to be dissolved to release it at the granular level.

 

Charles

Edited October 27, 2022 by cmjlab

[cmjlab]

So having failed at the ethanol, I then proceeded to boiled distilled water. I did a smaller amount of Barium Chlorate this time, as I did not want to lose a pound of what I have if the expiriment failed.

 

I took 100g, in a glass jar and poured in small amounts of boiling distilled water until it mostly all dissolved. I continued stirring and it eventually all dissolved, leaving a cloudy 1/2" layer at the bottom of the jar (which I took to mean it was a "saturated" solution of Barium Chlorate, and was on the verge of falling out of suspension at the bottom where cooler water was). I filtered the liquid twice through coffee filters, and to my surprise, nothing precipitated out even though the temperature of the solution had dropped substantially.

 

So I put the fluid in the freezer and checked again in two hours. Again, nothing had precipitated out, and the water was ice cold, but not yet frozen.

 

I left it over night, and of course it's frozen solid now. As it thaws slowly (4 hours and less than a tablespoon of liquid yet), it appears that there are now white particles floating in the liquid. However a majority of the liquid is still frozen solid, so I'm unsure if it crystallized at all, or just precipitated back into a powder that appears to insulate the ice from melting very quickly. It's admittedly only 65 degrees out, but I wouldn't think that'd slow down the thaw much.

 

Charles

[50AE]

I made Ba(ClO3)2 during my pyro years with MMO anode straight from barium choride electrolysis, but as warned from other people, 24h of electrolysis killed the anode - visually it was okay, but it stopped conducting current.

[justvisiting]

My suggestion costs nothing to try and will absolutely give 'some' success without wasting anything.

[cmjlab]

JustVisiting - I intend to try your method next.

 

I am however a little surprised at how even after cooling a saturated solution of Barium Chlorate (and before freezing it), that there was zero precipitation that occurred. The water was Ice Cold at that point, but still crystal clear. I'm no chemist but I thought for sure it would precipitate some crystals at that point.

 

It is possible since I did not measure the amount of water added, that perhaps it wasn't actually saturated, but I followed the normal (non-scientific) method of adding small amounts of boiling / distilled water till no more dissolves, then repeat, until ending with a clear solution.

 

Do you recall how long it took for the chlorate to begin to form crystals on the string?

 

Based on my experience with lack of precipitation, and you're success with the string, I wonder if it doesn't require some seed material to "kickstart" the crystallization out of solution (in your case - the string".

 

Charles