Arthur Posted March 22, 2015 Posted March 22, 2015 The iwaki pumps I used to use (in photo labs) would pump 30% sulphuric acid and other strong chemicals inc those that eat stainless! we used both Bellows pumps (for volumetric replenishment-these pump a calibrated amount per stroke or second,) and magnetic pumps for continuous recirculation. If you want to use a cell to chlorate completion then use the K salt -it's simpler. BUT if you want to run a replenished system or an auto system to perc then start with the Sodium salt having the perk as sodium salt means that you can control where it will crystalise out.
Titanium Posted March 24, 2015 Posted March 24, 2015 Hey,I still have lots of Potassium chlorate and perchlorate, but wanted to try my luck with electrolysis.I made MnO2 on Titanium electrodes (by using Mn(NO3)2) and electrolyzed a saturated KCl-Solution using an MnO2 on titanium anode and Titanium cathode with 5V and 24A.I let it run several hours and from time to time the solution got more and more yellowish.After that I boiled the solution down until it got fully saturated and put it in the freezer to cool down.Many needles formed which I filtered out and washed with Ethanol.But it seems like there isn't any chlorate in it, I tested it by mixing with dextrose, but it doesn't burn, also mixed with Mg it burns not faster than Mg alone.Has anyone an idea why no chlorate is produced?
Mumbles Posted March 24, 2015 Posted March 24, 2015 Sounds like your homemade electrode isn't working, or you didn't let it run nearly long enough. Despite what some internet sources will tell you, creating anodes suitable for chlorate electrolysis is more complicated than just making any old MnO2 coated substrate. A chemical test for chlorate, which are described in this thread, will give you a better answer. There will be a big difference in how to solve your problem knowing if you are in fact forming any chlorate (aka too short of an electrolysis time), or are just electrolyzing water (bad anode).
Titanium Posted March 25, 2015 Posted March 25, 2015 (edited) I think my electrode should work, because a few seconds after I turned on the power supply I smelled heavy chlorine odor.The strange thing is, that this solution bleached very strong, the brown coffeefilter was bright white a few seconds after I started filtering.Is it maybe possible, that a strong solution of KClO was made and not converted to KClO3 and KCl because of the cell not being hot enough?It's not very warm outside (around 10° C) maybe this is the problem? Edited March 25, 2015 by Titanium
Mumbles Posted March 25, 2015 Posted March 25, 2015 It is also entirely possible that your solution of KClO was not converted to KClO3 because you only ran it for a few hours.
Arthur Posted March 25, 2015 Posted March 25, 2015 Even assuming your anode is perfect with 100% current efficiency the production of chlorate is slow and demands many amp hours. MOst people seem to need to run a cell at HOT (70c) by electrolysis heating for close to a week before they have product. Do some basic calculations of amp hours needed to completely convert the chloride to chlorate then try to run for that many amp hours. You would be far better using a proven DSA/MMO anode.
Titanium Posted March 25, 2015 Posted March 25, 2015 Ok thank you both, I calculated it using the formula on: http://www.oocities.org/capecanaveral/campus/5361/chlorate/table54.htmlBut it's for NaCl solutions, KCl should be shorter, so I let it run for like 8.5 hours instead of 9.5, but it doesn't work very well.Maybe I should say that my cell is really small scaled so it should only need some hours.I'm now trying my luck with nearly the same volume of liquid but in a smaller container, so it has a smaller surface and don't looses temperature as fast as the other cell.Now it really gets warm, my other cell had maybe 15°C, but now I would say it's over 50-60°C.I know that for example MMO would work far better, but I had all materials here except for the titanium, which was really cheap and I wanted to give it a try.I hope it works better now with higher temperature, if not I must look where to get an MMO electrode.But there is no hurry because I still have 50lbs of KClO3 and 50lbs of KClO4 here because of the new regulations here in europe, maybe in some time it will be empty and here in europe it tends to be harder and harder to do our hobby
Arthur Posted March 25, 2015 Posted March 25, 2015 Over the years there have been different scales of trial production plant, from 200ml to 200litres. Usually the current in the cell is enough to keep it above 50c, below that the production is largely hypochlorite (bleach -hence decolouring the filter paper) probably getting the temperature UP will change the reaction enough to create chlorate.
WSM Posted March 26, 2015 Posted March 26, 2015 Hey,I still have lots of Potassium chlorate and perchlorate, but wanted to try my luck with electrolysis.I made MnO2 on Titanium electrodes (by using Mn(NO3)2) and electrolyzed a saturated KCl-Solution using an MnO2 on titanium anode and Titanium cathode with 5V and 24A.I let it run several hours and from time to time the solution got more and more yellowish.After that I boiled the solution down until it got fully saturated and put it in the freezer to cool down.Many needles formed which I filtered out and washed with Ethanol.But it seems like there isn't any chlorate in it, I tested it by mixing with dextrose, but it doesn't burn, also mixed with Mg it burns not faster than Mg alone.Has anyone an idea why no chlorate is produced? The first run of a KCl cell seldom produces much, if any, KClO3. Now if you take that electrolyte and dissolve as much KCl as will dissolve at room temperature and run it again, I suspect much more KClO3 will be produced. If you use an ammeter, run the recharged cell till the current drops to about half the peak current observed, and I expect you'll see MUCH more chlorate produced and drop out without boiling or chilling (or any other extreme measures) and collect on the bottom of the cell. If you try this, report back and tell us of your experience. WSM
WSM Posted March 26, 2015 Posted March 26, 2015 Ok thank you both, I calculated it using the formula on: http://www.oocities.org/capecanaveral/campus/5361/chlorate/table54.htmlBut it's for NaCl solutions, KCl should be shorter, so I let it run for like 8.5 hours instead of 9.5, but it doesn't work very well.Maybe I should say that my cell is really small scaled so it should only need some hours.I'm now trying my luck with nearly the same volume of liquid but in a smaller container, so it has a smaller surface and don't looses temperature as fast as the other cell.Now it really gets warm, my other cell had maybe 15°C, but now I would say it's over 50-60°C.I know that for example MMO would work far better, but I had all materials here except for the titanium, which was really cheap and I wanted to give it a try.I hope it works better now with higher temperature, if not I must look where to get an MMO electrode.But there is no hurry because I still have 50lbs of KClO3 and 50lbs of KClO4 here because of the new regulations here in europe, maybe in some time it will be empty and here in europe it tends to be harder and harder to do our hobby Okay, so which Country do you call home? Are there restrictions sending electrodes by post? WSM
WSM Posted March 26, 2015 Posted March 26, 2015 (edited) I think my electrode should work, because a few seconds after I turned on the power supply I smelled heavy chlorine odor.The strange thing is, that this solution bleached very strong, the brown coffeefilter was bright white a few seconds after I started filtering.Is it maybe possible, that a strong solution of KClO was made and not converted to KClO3 and KCl because of the cell not being hot enough?It's not very warm outside (around 10° C) maybe this is the problem? A strong solution, to be sure! When KCl solution is running in a proper chlorate cell, the solution becomes a very strong mixture of K+,Cl-, OCl-, HOCl- and ClO3-. The percentages of all the parts vary, depending on myriad factors at any one point in time, but they're controllable (to some degree) if we understand the process and change the parameters as needed. This is how industry drives the CE of commercial cells to well above 90% (and, properly done, so can we). Edit: I agree with others here, depending on all the other factors (including the viability of your home made electrode), timing may be the issue with your cell. Try running it longer, PLUS recharging the liquor with more KCl solution will probably create much more chlorate. Starting with recharged electrolyte, the cell has the advantage of all the precursors present, rather than spending a lot of energy creating them. Try it again and see how it works. WSM Edited March 26, 2015 by WSM
Titanium Posted March 26, 2015 Posted March 26, 2015 (edited) Over the years there have been different scales of trial production plant, from 200ml to 200litres. Usually the current in the cell is enough to keep it above 50c, below that the production is largely hypochlorite (bleach -hence decolouring the filter paper) probably getting the temperature UP will change the reaction enough to create chlorate. Yes, I'm hoping so, now the temperature is much higher, it's now running the ninth hour because I turned it off over night. The first run of a KCl cell seldom produces much, if any, KClO3. Now if you take that electrolyte and dissolve as much KCl as will dissolve at room temperature and run it again, I suspect much more KClO3 will be produced. Thank you for this information, I didn't know that, I will try that out Okay, so which Country do you call home? Are there restrictions sending electrodes by post? WSM I call Germany my home, with probably the most pyrophobic government ever, in shipping Electrodes there shouldn't be a big problem. I talked about the problem of the new EU-laws saying that it's forbidden to sell for example KClO3 and KClO4 to privates and checking nitrate buys for "suspicious transactions" since September 2014 Here in germany even buying oxidizers or some other chemicals is partly unpossible, but it was possible to chemicals in some other EU countries and ship to here without a problem.But now the whole EU is toughening the laws especially for oxidizers, but also fore "precursors" of HE's like Hexamine and various acids Try running it longer, PLUS recharging the liquor with more KCl solution will probably create much more chlorate. Starting with recharged electrolyte, the cell has the advantage of all the precursors present, rather than spending a lot of energy creating them. Try it again and see how it works. WSM I will try it, I will post how it goes Edited March 26, 2015 by Titanium
WSM Posted March 27, 2015 Posted March 27, 2015 I call Germany my home, with probably the most pyrophobic government ever, in shipping Electrodes there shouldn't be a big problem. I talked about the problem of the new EU-laws saying that it's forbidden to sell for example KClO3 and KClO4 to privates and checking nitrate buys for "suspicious transactions" since September 2014 Here in germany even buying oxidizers or some other chemicals is partly unpossible, but it was possible to chemicals in some other EU countries and ship to here without a problem.But now the whole EU is toughening the laws especially for oxidizers, but also fore "precursors" of HE's like Hexamine and various acids I live in the Western US. I Imagine the way things are where you live are only a penstroke away for us. All it takes is a group of over-zealous government officials to cause a massive loss of personal freedoms for all. There is anode material available in the US for not too much money. That may be true for Europe as well. If you can't find it there, I'll share links to it here. WSM
Titanium Posted March 27, 2015 Posted March 27, 2015 (edited) Yes, the problem is, that governments thinks that the are the only one who can think and threats all the citizens like childs.I looked for MMO electrodes here in Europe, but compared to US they are much more expensive (found a shop in UK that sells 2,5x2,5cm MMO coated Ti for around 55$ each excluding shipping).So I think I order in the US, I think I'm buying on the amateur chemist store since they are much cheaper(even with shipping) Edited March 27, 2015 by Titanium
Titanium Posted March 28, 2015 Posted March 28, 2015 The cell seems to work quite good with higher temperature and resaturating.The whole bottom was full of a thick layer of crystals even when it was hot, so I filtered and washed with distilled water to get rid of the violett(I would say KMnO4) contamination on the crystals.I mixed a few milligrams with Sugar and it burned quite good, also with a few milligrams of Mg there was a nice *poof*But because I still have more than enough KClO3 and I want to make other chlorates that are a lot more soluble, I ordered an 2inch x 6inch MMO electrode from the US.So MnO2 electrodes work quite good in making chlorates but the problem is that the product is contaminated with some Mn(VII), that (in the case of KClO3) can easily be washed of with ice water
Arthur Posted March 29, 2015 Posted March 29, 2015 Commercial production relies on removing some impurities before proceeding to perc. Usually in a sodium (professional) cell unwanted items are removed from the sodium chlorate liquor by precipitation
WSM Posted March 29, 2015 Posted March 29, 2015 Commercial production relies on removing some impurities before proceeding to perc. Usually in a sodium (professional) cell unwanted items are removed from the sodium chlorate liquor by precipitation Do you have any details that we can apply to our amateur cells (the more complete and specific, the better)? Thanks in advance... WSM
Titanium Posted March 30, 2015 Posted March 30, 2015 Yes, that would bei great, because I think it's a bit dificult to remove the exact ammount of, for example NaCl if NaClO3 has higher solubility.Is there any way to calculate this to loose as less in this case NaClO3 as possible?
Arthur Posted March 30, 2015 Posted March 30, 2015 http://www.typhoonguitars.com/oxidizer/chlorate/further/jesfeb69.pdf among lots of others
WSM Posted March 30, 2015 Posted March 30, 2015 http://www.typhoonguitars.com/oxidizer/chlorate/further/jesfeb69.pdf among lots of others An excellent reference. Do you have anything that details production of purified sodium chlorate (low chlorides, specifically) for use as feed stock for the perchlorate cells? WSM
Titanium Posted March 30, 2015 Posted March 30, 2015 (edited) Thank you, the purification of NaClO3 and Ba(ClO3)2 for perchlorate cell is also something I'm interested in Edited March 30, 2015 by Titanium
Arthur Posted March 30, 2015 Posted March 30, 2015 First remember that professional cells use sodium chloride brine and precipitate the required product with the chloride salt of the required cation.
WSM Posted March 31, 2015 Posted March 31, 2015 Thank you, the purification of NaClO3 and Ba(ClO3)2 for perchlorate cell is also something I'm interested in I'd suggest treating the two you mention completely separately. For example, some have described making Ba(ClO3)2.H2O from KClO3 and BaCl (if I remember correctly), but making and purifying NaClO3 is an altogether different mechanism. As to making barium perchlorate (if I understand you correctly), the reason escapes me. It will serve no useful purpose in pyrotechnics that I'm aware of due to its strongly hygroscopic nature. WSM
WSM Posted March 31, 2015 Posted March 31, 2015 First remember that professional cells use sodium chloride brine and precipitate the required product with the chloride salt of the required cation. Are you suggesting making sodium chlorate (even contaminated with chloride) and using that as feed stock for perchlorate cells? Most references infer that chloride-free sodium chlorate solution would be preferred for perchlorate cells to prevent damage to the anodes (especially platinum and, to some degree, LD). WSM
Titanium Posted March 31, 2015 Posted March 31, 2015 I'd suggest treating the two you mention completely separately. m. As to making barium perchlorate (if I understand you correctly), the reason escapes me. It will serve no useful purpose in pyrotechnics that I'm aware of due to its strongly hygroscopic nature. Yes, I mentioned it completely separately.The good thing with Barium perchlorate is, that BaSO4 is insoluble and so i can make Ap with Ammonium sulfate and Ba(ClO4)2 and don't have a Sodium contamination like in the route with NaClO4 Corrosion of Platinum would also be the problem why I would like to get chloride free chlorate.
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