Arthur Posted October 8, 2009 Posted October 8, 2009 OK side question! Has anyone electrolysed Barium Chloride to chlorate? Does it work?
Ralph Posted October 8, 2009 Posted October 8, 2009 barium is maent to be a poison for MMO and im not going back to graphite
Ventsi Posted October 9, 2009 Posted October 9, 2009 Swede: I found out the crystals were merely undissolved NaCl and the fine film of xtals was the slat additive to make it flow better[think Cab-O-Sil]. The cell was stopped after 11 days and the liquor is resting inside a 1 gal. bottle.I'm still in need to get some KCl , just too low on money... Arthur: here is one site- http://www.geocities.com/CapeCanaveral/Cam...ate/barium.html
Swede Posted October 9, 2009 Posted October 9, 2009 Swede: I found out the crystals were merely undissolved NaCl and the fine film of xtals was the slat additive to make it flow better[think Cab-O-Sil]. The cell was stopped after 11 days and the liquor is resting inside a 1 gal. bottle.I'm still in need to get some KCl , just too low on money... One thing that's true with a sodium cell... you can always decant, or filter, and leave any solids behind, because by definition, they are not chlorate or perchlorate, both highly soluble when the liquor is hot. I'd need to do some math, but I'm not sure if it is possible to start with saturated NaCl and end up with a solution of chlorate that is beyond saturation, resulting in NaClO3 xtals forming. I think all you'll end up with should just be a nice, clear liquor, unless you chill it. The MW of the chlorate is about twice that of the chloride, and the solubility of the chlorate is more than 2X as much on a mass basis, so everything should stay dissolved.
tentacles Posted October 23, 2009 Posted October 23, 2009 (Copied from my post on scimadness)There has recently been some discussion on the passfire board, reminiscing about the somewhat legendary Swedish perchlorate. It is known to be the absolute best perchlorate in pyrotechnic compositions - particle size shape and distrubution just perfect. At any rate, someone mentioned a typical 1992 assay: 99.8 % KClO40.03 % KClO30.01 % KClInsolubles less than 0,01 %Moisture less than 0,02 %Neutral pHParticle distribution: 100 % passing 140 mesh, 65 % passing 230 mesh and 45 % passing 325 mesh. It is purely anecdotal, but clearly swede's under 10ppm would be very suitable for pyrotechnic use. Here's something a LOT less anecdotal: Barium and Chemicals and Hummel both distribute military spec. product and that potassium perchlorate spec. hasn't changed since at least Sept. 1962 and perhaps the early 1940s: It's not a hard spec to meet; purity of only 99.0% and 0.1% KClO3, -0-% hypochlorites with easily met particle size standards: http://www.tpub.com/content/MIL-SPEC/MIL-P/MIL-P-217A/ Swede, there has been some comparison testing between the various brands of perc, it might be interesting to send Dan C a sample of yours to add to the test as an example.
Swede Posted October 23, 2009 Posted October 23, 2009 So the question is finally answered. Mil-spec perchlorate can be up to 0.1% chlorate, which is 1,000 parts per million. With the NPAA test being good down to 20 or so PPM, anything that checks clean with the NPAA test can be considered pyro ready perchlorate. And this makes sense to me. At 0.1% chlorate, you have 1,000 PPM which sounds like a lot, but from another perspective, it is 1 gram of chlorate in a kilogram of perchlorate. Chemically, I don't think this concentration will cause any problems. Even so, it should not be hard to drive the chlorate down to below 100 PPM ( 0.01% chlorate) with standard hobbyist cleanup methods. SO2 gas works, from potassium metabisulfite from a brew shop. The hard part is obtaining intimate contact of the evolved SO2 gas when you add the metabisulfite to an acidic solution of raw electrolytic, hot perchlorate. SO2 gas is inversely soluble with temperature, but without higher temps, the perc doesn't dissolve worth a damn. I think the answer might be to combine the perc with the metabisulfite in cold acidified water; the metabisulfite evolves SO2 gas which dissolves with ease. As the temperature comes up, the perc dissolves, contamination is reduced, before the SO2 gas is driven off by the higher temperatures. There's a LOT of room for experimentation in perchlorate cleanup. Metabisulfite is just one way to do it.
Mumbles Posted October 23, 2009 Posted October 23, 2009 Another way might be to treat it in a sealed vessel. It can be heated and the SO2 above the solution would be redissolved as it is used up. Stirring would also help. Even a 5 gallon bucket might be sufficient to contain the gas. I know there is a thread over on Sciencemadness about making sulfuric acid by burning sulfur and KNO3 inside of a sealed bucket with some water in the bottom.
Swede Posted October 24, 2009 Posted October 24, 2009 I like that simple concept, Mumbles. A container with a lid that will not seal to the point of bursting if the solution gets too hot and boils. I've got a PTFE coated coil immersion heater. On a large scale, I'm picturing heating, vigorous mechanical stirring to keep the surface agitated, and a bucket lid on a 5 gallon (or larger) PE or better yet polypropylene container. Dump the chems in, add water, and run a cycle like a washing machine. Sodium would make the job even easier, given the high solubility of sodium perchlorate. Clean it up in bulk, then execute the conversion to pull potassium perchlorate solid out of the system.
Ventsi Posted November 5, 2009 Posted November 5, 2009 (edited) I'm wondering, how efficient is magnetite for chlorate production?I know it corrodes slowly but it might be useful in little do-dad experiments.Anyone have any info? I have a couple small-medium rods waiting for a use... Edited November 5, 2009 by Ventsi
tentacles Posted November 6, 2009 Posted November 6, 2009 Magnetite has quite low efficiency - dann or xenoid on scimadness did some experiments with it and was only able to produce chlorate when pH controlled. I think he got something along the lines of 17% eff. You can do better with graphite and no pH control.
Swede Posted November 6, 2009 Posted November 6, 2009 It's been a while since I've done any "real" work. With fall finally here, I'm back at it, setting up both the bucket cell and the T-Cell for runs with data collection, and I'm especially anxious to test my lead dioxide anode. One of the real hassles of these cells is the simple act of circulation. I've used a bubbler in the past. With potassium salts, when the liquor is finally saturated, the cool air exiting the tube to bubble out will cause crystallization and jamming of the tube, and even when cleared, it will re-clog within an hour or two. Not good. I decided to make a mechanical stirrer similar to the one on my lead dioxide plating rig. I started by making a combination PVC/PTFE fitting which will act as a bearing. Hopefully it will seal decently. The white part is PTFE pressed into the CPVC body of the fitting: http://www.5bears.com/perc/mstir01a.jpg A suitable DC motor was found in my junk box, and mounted on an aluminum angle: http://www.5bears.com/perc/mstir01.jpg A shaft adapter was turned from stainless steel, one end to grip the motor (metric) and the other to grip a teflon round shaft... http://www.5bears.com/perc/mstir02.jpg At the bottom, the shaft was drilled and tapped 10-32 for a little titanium sheet paddle. The screw is also titanium. These materials are all compatible with the cell electrolyte... http://www.5bears.com/perc/mstir04.jpg Finally, a removable PVC mount was fabricated. What this thing will do is allow me to remove the stirrer and mount the whole thing over another cell, like the bucket cell, by using a stainless shaft, using a typical chemistry stand and hardware... the same sort of thing you'd use to support a complex organic chem apparatus... http://www.5bears.com/perc/mstir05.jpg At 6 volts, I'm getting gobs of torque from this thing. I found I had to have a pretty sloppy fit of shaft to bearing to avoid overheating, but I'll put up with gassing and salt creep if it gives me a good stirring action. I think what I will definitely do is put a fuse inline with the motor. On a lab power supply, it's drawing 300 mA at 6V. If for some reason the bearing binds up, and the motor slows down, or it jams with xtals in some manner, the current will soar and should blow the fuse. I'm thinking a 1 amp slo-blow should do the trick.
WSM Posted November 8, 2009 Posted November 8, 2009 Very nice work, Swede. I wonder if fluorosilicone grease would help reduce friction in this setup? If you can't find any and would like to try some, let me know. I may have a little tube or tub of it I could send over for you to try. Let me know. Thanks for sharing and keep up the good work. WSM
mike_au Posted November 9, 2009 Posted November 9, 2009 The cell walls might be a bit to thick for it, but have you considered a magnetic stirrer like they use for circuit etching tanks?
50AE Posted November 10, 2009 Posted November 10, 2009 I started making chlorate again and it works great, I have an issue with the wiring though. The space between the electrodes is very small, so I don't have much space to connect the wires properly. And a tiny difference in the resistance makes the amps drop drastically.I'll have to search for some good clamps maybe.
Bonny Posted November 10, 2009 Posted November 10, 2009 I started making chlorate again and it works great, I have an issue with the wiring though. The space between the electrodes is very small, so I don't have much space to connect the wires properly. And a tiny difference in the resistance makes the amps drop drastically.I'll have to search for some good clamps maybe. How close together are your electrodes? just get some pan head bolts and mount the wires on the outside surface. You could drill new holes in the elctrode shanks and offset the bolt holes (1 higher than the other, or off to each side, so the heads do not touch)
Arthur Posted November 10, 2009 Posted November 10, 2009 You should only need a few volts for chlorate production so a piece of sticky tape should do for insulation, possibly even some paint!
patsroom Posted November 11, 2009 Posted November 11, 2009 (edited) It's been a while since I've done any "real" work. With fall finally here, I'm back at it, setting up both the bucket cell and the T-Cell for runs with data collection, and I'm especially anxious to test my lead dioxide anode. One of the real hassles of these cells is the simple act of circulation. I've used a bubbler in the past. With potassium salts, when the liquor is finally saturated, the cool air exiting the tube to bubble out will cause crystallization and jamming of the tube, and even when cleared, it will re-clog within an hour or two. Not good. I decided to make a mechanical stirrer similar to the one on my lead dioxide plating rig.snip snip Just a quick snip and it was done. Hi Swede, I always read with interest when it comes to your work here. As for the data collection I would love to hear about that when it is in.I would also like to see a new picture of the Lead Dioxide Anode and the specs to it as well. (I think you know why.) But just as important does it work well at a cost that will be well in reach for us all.Good ideal about using a stirrer for the circulation and I will have to try that and see if there is a decrease in time for producing chlorate.....Pat Edited November 11, 2009 by patsroom
Swede Posted November 12, 2009 Posted November 12, 2009 Thank you for the kind words. The original concept for the data collection scheme was to plot basic cell parameters throughout a run, in an attempt to determine "End of run" conditions not based upon chloride concentration (expensive and and a hassle) but upon the hypothetical relationship of voltage vs current as the chloride depletes. With constant current conditions, the voltage will vary over the run, and likewise, with constant voltage, the current will vary. I normally run CC, making it easier to determine efficiency, and I've noticed the voltage varying in a concave curve. Starts moderate, drops, then climbs toward the end. If the relationship of voltage and current are repeatable, then the end of run state can be determined mathematically, making it greatly simplified. Plus, I think it'll be cool to have an accurate plot of all cell parameters except pH in a chart-recorder format. On the stirrer - in a pH controlled cell, the route to chlorate is via the 6-electron "bulk" reaction, and does not occur at the electrodes, but rather in the cell volume itself. The immediate area around the anode is highly acidic; that near the cathode is quite basic, and a good mixing should increase the efficiency of the cell. It also distributes heat better. Without good circulation, the heavy salt concentrations create a powerful temperature gradient. Hot salt water is less dense, remains at the top, is exacerbated by the normally top-positioned electrodes, and the bottom of the cell remains cool. The next run in about 4 days will be bucket cell, data collection, using pure KCl to start. If the bucket cell concept works, then the LD anode will be tried... finally, after almost a year.
50AE Posted November 12, 2009 Posted November 12, 2009 I have 4mm space between both electrodes. I think I could drill some small 2.5mm holes and put small screws to tighten the connections.
Swede Posted November 12, 2009 Posted November 12, 2009 I have 4mm space between both electrodes. I think I could drill some small 2.5mm holes and put small screws to tighten the connections. Can you bend the shanks a tiny bit to give it a "rabbit ear" look? That should give you room for the hardware, but your mounting might prohibit the bending. 4mm is a tight spacing. Effective, but tight. If it works for you and there is no possibility of shorting, it'll be beneficial.
Ventsi Posted November 13, 2009 Posted November 13, 2009 WOW, I just found 40g of Ammonium Bicarbonate my grandma sent me from Europe for cooking purposes. Can this be turned into AP by double replacement with KClO4? In your face customs!
Ventsi Posted November 13, 2009 Posted November 13, 2009 21g/100ml 100*C doesn't sound too bad I'm asking if the reaction will work is all. The KClO4 what turns into the more soluble ammonia salt will be replaced by more KClO4 and so on , so it might take a while, but in theory should work.
scarbelly Posted November 13, 2009 Posted November 13, 2009 How are you planning on separating out the NH4ClO4 or the Potassium Bicarbonate? Both of them will be soluble in water.
Ventsi 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 ...
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