scarbelly Posted November 13, 2009 Posted November 13, 2009 Nuts! Their solubility is pretty freaking close. My plan has foiled again, unless someone can suggest a way this is actually possible ...Yeah, you'd need to find something to scavenge out the K+ ion, and as far as I've learned in chem and AP Chem, all potassium salts are soluble... If you find something, you'll need to be sure the cation in that molecule will also be able to precipitate out. I don't think this is the way to go about approaching synthesis of ammonium perchlorate unfortunately.
Ralph Posted November 13, 2009 Posted November 13, 2009 I can sujest a way that will work and work very well as far as safety goes well lets just say this probably belongs on the do not try list. Take concetnrated sulfuric acid and KClO4 and distil off the highly explosive perchloric acid than react it with the ammonium bi carbonate. In theory nice and simple in practice very difficult to do on any scale other than industrial
scarbelly Posted November 13, 2009 Posted November 13, 2009 Reacting the perchloric acid and ammonium bicarbonate is a gas evolution reaction right? The bicarbonate becomes H2O and CO2? That actually sounds pretty doable for anyone with decent glassware and proper safety preparations.
Ralph Posted November 13, 2009 Posted November 13, 2009 its the distilling of a High explosive that is extremely unstable at many of its states of hydration not to mention its tendancy to explode when it comes into contact with organic material
scarbelly Posted November 13, 2009 Posted November 13, 2009 its the distilling of a High explosive that is extremely unstable at many of its states of hydration not to mention its tendancy to explode when it comes into contact with organic materialYeah I take back what I said. Sounds dangerous and not really worth the risk; especially considering you can buy ammonium perchlorate
Mumbles Posted November 13, 2009 Posted November 13, 2009 You could potentially generate a solution (weak please) of perchloric acid by adding tartric acid. It's the only insoluble potassium salt I know of, at least more insoluble than perchlorate.
Swede Posted November 18, 2009 Posted November 18, 2009 The bucket cell (2.5 gallons) is an hour or so away from startup. I have 10 liters of pure KCl ready to go... no starting with used electrolyte for this run, which will be a data-collection run. 2 samples per second of temperature, voltage, and current, will allow 2 week's worth of data to be written to an 8 gig USB memory stick. One of the problems is the cold... it has gotten chilly, and I need to keep the KCl solution warm (40 C) to keep it dissolved. Once in the cell, I need to jack the current quickly to keep the temperature up, and prevent KCl from crystallizing. If it does, initially, I assume that it will enter the solution again as the temperature stabilizes. pH control will be via 16% HCl, a Hanna dosing pump, and the timer I built and outlined in a blog entry. I cannot track pH like the other data elements due to poisoning issues with the pH electrode, but I will do my best taking manual samples on a regular basis, and doing a quick pH check. Milwaukee Instruments produce inexpensive, but very nice quality, meters and probes. Their SM-101 tester which has manual ATC is a good one. The standard cheap probe they offer is their MA-911, a yellow, gel-filled probe, that has worked very well for me for quite a while. One big disappointment - there was a guy offering sugar-fine KCl on eBay, very nice looking stuff, $25 for 25 pounds shipped, but the reason it flows so fine is that it is FULL of some sort of silicate or other flow agent that is not soluble. The KCl dissolves nicely, but leaves behind the insoluble crud, and it requires serious filtration. I'll continue to go with the Diamond Crystal KCl nuggets. This is the guy - it is NOT high purity: eBay KCl seller
50AE Posted November 19, 2009 Posted November 19, 2009 I found good clamps and the cell is kickin' . The current is between 6-7A and for two weeks of run, I already have 400g of high purity KClO3, chloride free. One thing I discovered about chloride contaminated chlorate though - it will oxidize slowly. I think the chloride acts as a fire retardant. Here you get a second reason why you should purify your chlorate. Also, I think I can make a distinction between chlorate and chloride crystals, incase of putting too much KCl in the electrolyte. The KClO3 crystals seem to be more smooth and transparent, clean, whereas KCl crystals seem to be rough, white and caky.
Bonny Posted November 19, 2009 Posted November 19, 2009 I found good clamps and the cell is kickin' . The current is between 6-7A and for two weeks of run, I already have 400g of high purity KClO3, chloride free. One thing I discovered about chloride contaminated chlorate though - it will oxidize slowly. I think the chloride acts as a fire retardant. Here you get a second reason why you should purify your chlorate. Also, I think I can make a distinction between chlorate and chloride crystals, incase of putting too much KCl in the electrolyte. The KClO3 crystals seem to be more smooth and transparent, clean, whereas KCl crystals seem to be rough, white and caky. Do you wash and then dissolve/filter/recrystallize? I have only been washing mine "A-La-Swede" as I don't plan ATM to use any as chlorate, but to convert to perchlorate.As for electrolyte, when "recharging with KCl", I just add old electrolyte to a bucket with a good layer of KCL and let sit for several days, giving it a shake whenever I'm around. I then filter the liquid back into the cell.That way there is never any undissolved KCl to try and "distinguish" from chlorate. My cell runs ~20A and I now have at least 15Kg of chlorate and another run going now.
Mumbles Posted November 19, 2009 Posted November 19, 2009 Either way you should get that chloride out. It is a detriment to making perchlorate. If being used as chlorate, chloride sensitizes the chlorate by forming small amounts of KClO2, which is unstable in contact with organic materials.
Swede Posted November 19, 2009 Posted November 19, 2009 A decent washing should in theory drive the chloride contamination to about 0.8% max... at least that is what my experiments showed, something like 99.2% pure. Recrystallization takes the Cl- to nil, at least low enough so that silver nitrate test shows no precipitate - it is clearer than tap water. If I was going to use the chlorate for pyrotechnics and was concerned about chloride, and decided to recrystallize, I think it would save a lot of labor to set up a really big rig that would allow a massive recrystallization, on the order of several kilos per batch. Maybe a stainless steel boiler of 5 gallon capacity, executed outdoors, and a fridge or even a tub of ice water to bring the temp down to harvest. What comes out of that should be quite pure. For transformation to perchlorate, I don't plan on recrystallizing the chlorate - I'll go with the minute Cl- from well-washed chlorate. It might not be optimum, but I just cannot see recrystallizing 10 to 30 kilos if I can avoid it. The bucket cell is rockin' along! Success! I'll get some pics up. From a post on SMDB: My bucket cell adapter is running with a full data stream to a DATAQ electronic chart recorder, measuring voltage, current, and temperature. pH will not be possible due to the harsh environment, but I may execute a data run in the future using a cheap, disposable probe. The original plan was to hopefully correlate current and voltage so as to determine EOR (End of Run) conditions without having to measure chloride ion concentration. It is also the first use of an upgraded HCl delivery scheme using an Auber Instruments inexpensive timer. The cell is a 2.5 gallon HDPE bucket with 8.7 liters of pure KCl at 17.9% chloride, MMO anode, Ti cathode, and a good CC supply. The liquor was saturated at 50 degrees C, quickly added to the cell, and the current cranked quickly to keep the liquor hot. Here is where it gets interesting... With no cooling, the temperature at 40 amps CC climbed to as high as 76 degrees C. At this point, I pointed a small fan at the bucket, and this proved dramatic in lowering the temperature. Fan on, the temp drops to 55 degrees C. from nothing more than blowing air over the bucket. Between 55 and 75 degrees C, I noticed a very distinct correlation between temperature and voltage to maintain 40 amps. As the temperature climbed, the voltage dropped, and as the fan cooled the bucket, the voltage climbed once more. Several data points confirmed that higher temps require less power overall. Over approximately 18 hours, while the cell chemistry is still fairly young, 40.00 amps: V------------T5.26----54.175.16----55.815.05----59.715.05----60.494.99----61.744.96----70.634.84----70.864.80----71.024.76----76.32 A solid correlation that should have been obvious from other runs. It pretty much kills my notion that the voltage and current data can be used to determine EOR, unless a cell's temperature remains constant, which it rarely does. I'm certain that the literature on this process describes the reduced power requirement at higher temps, but I had not run into it before, or if I did, it went over my head. Temperature is your friend for the bulk process, just watch out for the materials! 75 degrees C is pushing it on a small HDPE bucket. And again, it shows that heating is always a problem when attempting a higher-current run measured in days rather than weeks. Probably more info than most need, but it is pretty interesting that higher temps reduce the power requirement... and that applies only to the bulk-reaction process from a pH controlled cell, AFAIK
50AE Posted November 19, 2009 Posted November 19, 2009 (edited) Bonny, I always do recrystallization. I don't count on washings only if I want to use this chlorate straight for pyrotechnics. My steps are : -Harvesting the crystalls from the cell.-Recrystallization-Washing with ice cold water once-Milling-Storing A test with lead nitrate shows no traces of chloride. Also, I use the recrystallization and washing water for electrolyte. Edited November 19, 2009 by 50AE
Bonny Posted November 20, 2009 Posted November 20, 2009 (edited) A decent washing should in theory drive the chloride contamination to about 0.8% max... at least that is what my experiments showed, something like 99.2% pure. Recrystallization takes the Cl- to nil, at least low enough so that silver nitrate test shows no precipitate - it is clearer than tap water. If I was going to use the chlorate for pyrotechnics and was concerned about chloride, and decided to recrystallize, I think it would save a lot of labor to set up a really big rig that would allow a massive recrystallization, on the order of several kilos per batch. Maybe a stainless steel boiler of 5 gallon capacity, executed outdoors, and a fridge or even a tub of ice water to bring the temp down to harvest. What comes out of that should be quite pure. For transformation to perchlorate, I don't plan on recrystallizing the chlorate - I'll go with the minute Cl- from well-washed chlorate. It might not be optimum, but I just cannot see recrystallizing 10 to 30 kilos if I can avoid it. Bonny, I always do recrystallization. I don't count on washings only if I want to use this chlorate straight for pyrotechnics. My steps are : -Harvesting the crystalls from the cell.-Recrystallization-Washing with ice cold water once-Milling-Storing A test with lead nitrate shows no traces of chloride. Also, I use the recrystallization and washing water for electrolyte. (If) I ever use any chlorate, I will dissolve and recrystallize. For my perc cell, I plan on trying it as is. I do 3 hard washings in cold (distilled) water which should reduce the chloride to a negligible amount. I will test the chlorate with silver nitrate before loading the cell to be sure. That won't be until spring though, as the weather here will be too cold to run a cell unless it is large and can have huge current pumped into it. I'm still trying to produce as much chlorate as I can before it's too cold. Edited November 20, 2009 by Bonny
50AE Posted November 27, 2009 Posted November 27, 2009 Has anyone succeeded making barium chlorate ? I'd really like to try. I don't want sodium though, it could be hard to wash.Maybe I could try by electrolysis of barium chloride with graphite electrodes ?
Mumbles Posted November 28, 2009 Posted November 28, 2009 Sodium chloride isn't extremely hard to remove as a contaminant, particularly if you don't create a super saturated solution. I found this reference, but don't have access to the journal. The abstract actually gives some decent information though. Details might be able to be inferred. http://pubs.acs.org/doi/abs/10.1021/ie051018r
Arthur Posted November 28, 2009 Posted November 28, 2009 Barium chloride will electrolyse, but the reaction is ineffecient because the Baruim ion can react in the cathode zone to form insoluble species which form suspended matter and both cloud the electrolyte and remove Barium from the process. There was a page on the geocities site but it has moved.
Bonny Posted December 9, 2009 Posted December 9, 2009 I now have my last batch of KCl from the 20Kg bag running in my cell...finally. The temperature outside has dropped to -24C (-11F I think). I just hope a lot of salt did not crystallize out. It has been running at a steady ~22A for several days and the cell is insulated and feels warm to the touch. I'll know in about another week. After my 5(?) runs, I think I'll end up with about 20kg+ of washed and dried KClO3.and I must say the MMO anode from Swede has performed perfectly. I should be receiving my mini Pt anode in the mail soon, so I'll try and get a cell set up over winter for the next step.
Lithium Posted December 10, 2009 Posted December 10, 2009 (edited) Hi, First post on the board. The page you are looking for has moved to www.oxidizing.110mb.com. The reference on Barium is in the Barium part.Could not current reversal be used to make Chlorates and Perchlorates that have the insoluble hydroxide problem. Connect a 555 timer to the cell via a simply reversing relay and use two pieces of MMO an electrodes. Reverse current every few minutes. With prices of MMO (Laserreds on ebay) as low as bare mesh Ti is seems easy. Barium chloride will electrolyse, There was a page on the geocities site but it has moved. Edited December 10, 2009 by Lithium
Ventsi Posted December 10, 2009 Posted December 10, 2009 (edited) Those seem a little too cheap. On the contrary, Swede, my Ti cathode has been getting a white powdery looking coating on this that is extremely hard to remove. Though I did manage to design a jar that gave me 0 salt creep, yes, tis' truth! Edited December 10, 2009 by Ventsi
Bonny Posted December 10, 2009 Posted December 10, 2009 Those seem a little too cheap. On the contrary, Swede, my Ti cathode has been getting a white powdery looking coating on this that is extremely hard to remove. Though I did manage to design a jar that gave me 0 salt creep, yes, tis' truth! I ge the same white stuff on my Ti cathode too. I haven't had any trouble cleaning it off though. Just use water and a hard sponge. You could also use steel wool.
Swede Posted December 10, 2009 Posted December 10, 2009 Agreed on the Ti cathode - they change color, get white smut, and can look pretty funky after a run, but can easily be cleaned by anything from steel wool, sandpaper, HCl, or kitchen cleanser. It would take years to eat away at the cathode to any serious degree. I don't know what the white stuff is. It makes me think of some insoluble calcium salts, perhaps from calcium in the tap water. If your water is hard, that might make excessive white encrustation. Distilled water is too expensive to use, IMO, for this process.
Bonny Posted December 10, 2009 Posted December 10, 2009 (edited) I don't know what the white stuff is. It makes me think of some insoluble calcium salts, perhaps from calcium in the tap water. If your water is hard, that might make excessive white encrustation. Distilled water is too expensive to use, IMO, for this process. I've been using distilled water the whole time and still get some white crap. If I wasn't on my last chlorate run (for likely quite a long time), I'd try tap water. Oh well too late now, I guess I ran some slightly more expensive chlorate, but if nothing else it should be purer anyway. Edited December 11, 2009 by Bonny
50AE Posted December 11, 2009 Posted December 11, 2009 Here's a video of my chlorate cell and setup : http://www.youtube.com/watch?v=_H-qtaWvqOE
Swede Posted December 11, 2009 Posted December 11, 2009 I've been using distilled water the whole time and still get some whire crap. If I wasn't on my last chlorate run (for likely quite a long time), I'd try tap water. Oh well too late now, I guess I ran some slightly more expensive chlorate, but if nothing else it should be purer anyway. I would use distilled if I wanted to get a purer product, like you said. It'd also be a good idea for a run where things like chloride are measured to a gnat's a**. Recrystallizations of small batches, too, for purity checks. But I don't know how you do it... I would use at least 10 to 15 gallons of distilled water per run for all the phases of the process, and I'm too lazy to drag all that distilled from the grocery store. I did check distilled grocery store water for chloride, and that at least was nil. I'd guess tap water, run through some basic filtration system, would be fine. I use water from a garden hose! It seems to work. There are always going to be minor contaminants, but I think technique trumps water source. 50AE - cool video! The music was appropriate, kind of a "sci-fi" tune. I like the basic setup, and I especially like the hacked PSU. You did some nice work with that. Your product looks good. It's funny, all of my cached chlorate is still in its fat crystal format. I have yet to mill or grind it down, except for a few grams once (mortar & pestle) for tests.
Bonny Posted December 11, 2009 Posted December 11, 2009 I would use distilled if I wanted to get a purer product, like you said. It'd also be a good idea for a run where things like chloride are measured to a gnat's a**. Recrystallizations of small batches, too, for purity checks. But I don't know how you do it... I would use at least 10 to 15 gallons of distilled water per run for all the phases of the process, and I'm too lazy to drag all that distilled from the grocery store. 10-15 gallons per run... Is that in your super cell? I use ~16l per run (in the cell), and that includes some recycled electrolyte, and then another 5-10l for washing each batch of 2-4 kgs.
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