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markx
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Quote: Originally posted by B(a)P  | I recently acquired some barium chloride with the view to convert it via electrolysis first to chlorate then to perchlorate.
I have a cell with a platinised titanium anode and titanium cathode.
Without doing a whole lot of research I jumper into the setup like I usually would for the sodium or potassium salts.
To aid with efficiency I usually add 1 g of potassium dichromate along with the chloride when I am first setting up. I failed to look into what might
happen when dichromate is added to a saturated solution of barium chloride. I didn't realise how insoluble barium dichromate was and I immediately got
a fine yellow precipitate in my previously clear solution.
Given barium dichromate is only soluble at 0.3 mg/L per 100 mL water will I have enough free dichromate to prevent the reduction of chlorate at the
cathode?
Has anyone else tried the electrolysis of barium chloride? If so what additives did you use?
This paper explores pH, temp and current density, but does not mention any additives, they used an MMO anode. They also used a rotating cathode which
is quite interesting. https://krc.cecri.res.in/ro_2006/044-2006.pdf
Any assistance would be greatly appreciated!
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Dichromates (also other additives) are not a must for chlorate electrosynthesis. I've never been a fan of the practice and have done just fine without
it. The mass production industry uses steel cathodes because of the cost factor and adds dichromate to hinder the reduction of chlorate on steel. This
is done to squeeze the last bit of possible efficacy out of their setup. In an amateur setting such efforts are often rather in vain and just
complicate the process by introducing more risk factors. Especially if one uses a titanium based electrode set...Ti already hinders the cathodic
reduction of chlorate and using dichromate is utter overkill. Soluble barium compounds are nasty enough poisons on their own, so introducing
dichromates to the setup seems a bit undue.
Do not intend to run a barium chlorate cell with an open top.....the spray is persistant and shall contaminate your premises. Also, producing barium
perchlorate is not of a practical purpose, as the salt is highly hygroscopic and shall be of little use in any compositions that do not include water.
[Edited on 27-9-2020 by markx]
Exact science is a figment of imagination.......
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B(a)P
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| Quote: Originally posted by markx |
Dichromates (also other additives) are not a must for chlorate electrosynthesis. I've never been a fan of the practice and have done just fine without
it. The mass production industry uses steel cathodes because of the cost factor and adds dichromate to hinder the reduction of chlorate on steel. This
is done to squeeze the last bit of possible efficacy out of their setup. In an amateur setting such efforts are often rather in vain and just
complicate the process by introducing more risk factors. Especially if one uses a titanium based electrode set...Ti already hinders the cathodic
reduction of chlorate and using dichromate is utter overkill. Soluble barium compounds are nasty enough poisons on their own, so introducing
dichromates to the setup seems a bit undue.
Do not intend to run a barium chlorate cell with an open top.....the spray is persistant and shall contaminate your premises. Also, producing barium
perchlorate is not of a practical purpose, as the salt is highly hygroscopic and shall be of little use in any compositions that do not include water.
[Edited on 27-9-2020 by markx] |
Thanks very much for the response markx. That is very interesting about the chromate/dichromate with regard to steel. It seems common that additives
are routinely used in chlorate cells with titanium cathodes from the reading and research I have done. I will try without for the barium salt and in
future with the sodium and potassium salt and see if there is a measurable difference in efficiency at the lab scale.
The end goal for the barium perchlorate is to make perchloric acid so the water will not be an issue.
I run my chlorate cell in my lab which is a portion of my garage. I have always had a gas scrubber on my chlorate cell due to the potential for
chromate/dichromate aerosols, so that will take care of the barium as well.
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yobbo II
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I would agree with B(a)P!
Dont obsess over additives.
Yob
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Fantasma4500
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so, mysteroisbchoice, 1.4kg in 4 days? how many amps is the device pulling in total? i usually just let my cell run with a total excess of NaCl
sitting at the bottom and the cell would trade out the NaCl with NaClO3 crystals, they grew really big and nice, big and rectangular. sadly NaClO3 is
illegal in europe these days, ive thought of Ba(ClO3)2 but it might form insoluble Ba(OH)2 at the electrodes or did i remember something wrong?
i recall there was one site with calculator on it called v2zkays or some shit, but its several computers ago, it featured calcium barium potassium
sodium and probably even rubidium, the only difference was relative to the molar weight of the molecule, how much chlorate it could contain per gramme
as for additives, chromate can be made as easily as just plonking in some NaHCO3 precipitated stainless steel chloride (316 SS is 18% chrome) the iron
will ppt out over time (which isnt an issue unless youre trying to decompose it thermally to perchlorate)
as for the thermal decomposition, what setup do you have for that? i remember dr lipton on YT did the whole thing with a heatgun and a small
refractory build and got .. well some results. but 80%+ yield? thats pretty wild, could vacuum maybe be used to increase yields or have you found some
catalyst? maybe if you have a solid setup you could try messing around with catalysts to really revolutionize the no-no's
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mysteriusbhoice
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| Quote: Originally posted by Antiswat | so, mysteroisbchoice, 1.4kg in 4 days? how many amps is the device pulling in total? i usually just let my cell run with a total excess of NaCl
sitting at the bottom and the cell would trade out the NaCl with NaClO3 crystals, they grew really big and nice, big and rectangular. sadly NaClO3 is
illegal in europe these days, ive thought of Ba(ClO3)2 but it might form insoluble Ba(OH)2 at the electrodes or did i remember something wrong?
i recall there was one site with calculator on it called v2zkays or some shit, but its several computers ago, it featured calcium barium potassium
sodium and probably even rubidium, the only difference was relative to the molar weight of the molecule, how much chlorate it could contain per gramme
as for additives, chromate can be made as easily as just plonking in some NaHCO3 precipitated stainless steel chloride (316 SS is 18% chrome) the iron
will ppt out over time (which isnt an issue unless youre trying to decompose it thermally to perchlorate)
as for the thermal decomposition, what setup do you have for that? i remember dr lipton on YT did the whole thing with a heatgun and a small
refractory build and got .. well some results. but 80%+ yield? thats pretty wild, could vacuum maybe be used to increase yields or have you found some
catalyst? maybe if you have a solid setup you could try messing around with catalysts to really revolutionize the no-no's |
I ran around 25 amps through the setup but now I have even better yields by running 35 amps with passive cooling + keep adding NaCl every 2 days and
little old me ran once and now I have in total 6kg of NaClO3 and nothing to do with it.
as for perchlorate synth using heat I use stove + pyrex dish which ive done many runs with around 20 and it tanks the heat like nothing taking even
temps of upwards of 500 Celsius for other experiments like KClO3 melting.
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Fantasma4500
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cast yourself some magnalium and grind that up into 80 mesh, should do well for some nice flares, for binder you can use hotglue heated with oil until
you get proper consistiency, PVC powder would help for brightness, NaClO3 also works well with silicon powder, hard to light but its very bright and
hot once it gets going, and of course the forbidden chlorate-oil binary - if youre brave.
aha... stove? does it seem that the exact temperature plays a significant role, and do you have any methods of eliminating ferrous contamination? back
when i was running chlorate cell i believe i had maybe 1kg of impure crystals sitting in a 2L plastic bottle of supersaturated chlorate solution at
room temperature - so like, 20x100g, 3kg i never got to purify? if you fancy crystals you can dump the saturated solution into a widemouthed coffee
thermocan with a crystal inside, throughly cleaned. once it slowly cools down you might get one large crystal out of it- one time i managed to produce
a 50mm wide crystal with alum, but mostly i will just get 20mm sized crystals, with chlorate solution you might wanna not dump in boiling hot
saturated solution, but the chlorate crystals are quite nice and rectangular
maybe you should go for producing some rocket engines, or try to turn that NaClO3 into NaClO4 and subsequently react that with NH4Cl and then
fractionally crystallize out the NH4ClO4? could be very profitable. reference the solubility curve of NaCl when in doubt.
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Benignium
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So I decided to try out a bromate cell.
After producing one batch of potassium perchlorate and another of sodium perchlorate, I decided that's enough of that and made a new electrolyte
comprising 507 grams of KBr and plain water, no additives. Initially everything was fine. Then, along with small crystals of bromate, some garbage
started to appear. Eventually there was so much solid stuff in suspension that the electrodes were completely obscured. The solid stuff that settled
on the bottom of the cell soon overwhelmed the stirring. With stirring gone, a lot more solids settled and suddenly current practically stopped
flowing. Upon investigation it turned out that inside a bromate cell the conditions are somewhat different. What happened exactly beats the shit out
of me. 
I managed to produce and isolate a whopping 63 grams of very pure potassium bromate. Even that is going to last me a long time, so it wasn't all for
nothing.
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mysteriusbhoice
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I have succesfully made NaClO4 and KClO4 using my homemade polymer composite substrate PbO2 anodes using a Ti current carrier since that MMO was
totally destroyed I turned it into a PbO2 anode and now its better than ever.
Heres a video of me making KClO4 from one of my earlier batches of NaClO4.
https://www.youtube.com/watch?v=o6pZUcMQmfc
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yobbo II
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Some reading for Bromate makers.
http://www.chlorates.exrockets.com/further/bromates.pdf
Yob
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