pyrojig Posted November 27, 2016 Posted November 27, 2016 If one where interested in making lithium perch, would there be a need to salt out the sodium perch 1st out of sol. ? (Either for proper weights , and or proper solvent that both it and its lithium salt can double decomp in .) , Or...., is there a salt of choice that is water soluble they can be mixed with the sodium perch in sol. To double decomp / drop out LI perch?If you where to drop out sodium perch ( out of sol.) refrigerate it , then what would be the best way to dehydrate it? Would you suggest desiccants , and what kind(non copper salts)?
WSM Posted November 28, 2016 Posted November 28, 2016 If one where interested in making lithium perch, would there be a need to salt out the sodium perch 1st out of sol. ? (Either for proper weights , and or proper solvent that both it and its lithium salt can double decomp in .) , Or...., is there a salt of choice that is water soluble they can be mixed with the sodium perch in sol. To double decomp / drop out LI perch?If you where to drop out sodium perch ( out of sol.) refrigerate it , then what would be the best way to dehydrate it? Would you suggest desiccants , and what kind(non copper salts)?When I get home, I'll look into it. WSM
Mumbles Posted November 28, 2016 Posted November 28, 2016 Do you think adding something to precipitate the excess sulfate or sulfuric acid might work? I was thinking something like barium or strontium chloride. The sulfates are essentially insoluble and would produce HCl which is already in the solution after acidification. They shouldn't interfere with the reaction either. I don't fully understand the reaction for indigo carmine, but it seems odd that sulfate would interefere. I don't really think of it as being particularly oxidizable or reducible
WSM Posted November 30, 2016 Posted November 30, 2016 (edited) Do you think adding something to precipitate the excess sulfate or sulfuric acid might work? I was thinking something like barium or strontium chloride. The sulfates are essentially insoluble and would produce HCl which is already in the solution after acidification. They shouldn't interfere with the reaction either. I don't fully understand the reaction for indigo carmine, but it seems odd that sulfate would interefere. I don't really think of it as being particularly oxidizable or reducible I reviewed the old analysis article describing the use of Indigo Carmine to determine the presence of chlorate, and the reference tells that Indigo can be used to determine chlorate or sulfite (also SO2), depending on your approach. One test is a reversal of the other, but the common component is the Indigo Carmine solution test reagent. I believe that when some chlorate is present, Indigo will determine the presence of sulfite or sulfur dioxide (by turning clear) just as well as sulfite or sulfurous solutions will help determine the presence of chlorates with the same result (by turning clear). It's a triangle of materials (Indigo Carmine, chlorate and sulfur dioxide) and the test can go either way. The other two chlorate tests I'm experienced with don't react to sulfur dioxide and so are better choices for testing for the presence of chlorates in sodium perchlorate solutions treated with sodium metabisulfite for purification purposes. Unless we can find a way to use Indigo in the presence of SO2 without interference, we'll need to search for alternative methods of chlorate detection in a sodium perchlorate solution. WSM Edited December 1, 2016 by WSM
WSM Posted December 1, 2016 Posted December 1, 2016 A couple years ago, I acquired a 35" (89 cm) long piece of heavy walled 6" (150 cm) diameter PVDF (Kynar) pipe on eBay. My thought was to make a high temperature reaction chamber for running a hot chlorate cell. The problem is the PVDF can't be solvent welded like PVC, and takes special, expensive welding equipment to weld it and stress relieve it after welding, in order to make a tank. My thought is to either make a tight fitting round disk (of thick PVDF sheet) to press into the bottom of the pipe, hoping to seal the bottom of the tank, OR, build an external framework to hold a compatible top and bottom plate to the ends of the pipe, to form a tank. The pipe section will be standing vertically on one end, and have piping running mainly through the flat plates rather than negotiating the curved sides of the pipe tank wall. A stand of some sort will add stability to the structure and rise it high enough to allow plumbing, electrode and sensor fittings to enter and leave the bottom of the tank as well as the top. This idea is developing and I'll alter the plans as needed as this progresses. WSM
WSM Posted December 1, 2016 Posted December 1, 2016 A couple years ago, I acquired a 35" (89 cm) long piece of heavy walled 6" (150 cm) diameter PVDF (Kynar) pipe on eBay. My thought was to make a high temperature reaction chamber for running a hot chlorate cell. The problem is the PVDF can't be solvent welded like PVC, and takes special, expensive welding equipment to weld it and stress relieve it after welding, in order to make a tank.My thought is to either make a tight fitting round disk (of thick PVDF sheet) to press into the bottom of the pipe, hoping to seal the bottom of the tank, OR, build an external framework to hold a compatible top and bottom plate to the ends of the pipe, to form a tank. The pipe section will be standing vertically on one end, and have piping running mainly through the flat plates rather than negotiating the curved sides of the pipe tank wall. A stand of some sort will add stability to the structure and rise it high enough to allow plumbing, electrode and sensor fittings to enter and leave the bottom of the tank as well as the top.This idea is developing and I'll alter the plans as needed as this progresses.WSM I need to get this set up and started to test the validity of the patent suggestions using MMO instead of platinized titanium anodes. If the patent idea works with DSA anodes (MMO) I should be able to accelerate my sodium chlorate production and move right into perchlorate production. I have great hopes for a wonderful Winter !!! WSM
lloyd Posted December 1, 2016 Posted December 1, 2016 (edited) My suggestion, considering the large expense and difficulty of even RUNNING your rig, would be to buy a low-cost titration rig, and be able to test pH to a gnat's ass of accuracy! Glassware is cheap! (space to set it up in the average shop, not so much <grin>) Lloyd Edited December 1, 2016 by lloyd
WSM Posted December 2, 2016 Posted December 2, 2016 My suggestion, considering the large expense and difficulty of even RUNNING your rig, would be to buy a low-cost titration rig, and be able to test pH to a gnat's ass of accuracy!Glassware is cheap! (space to set it up in the average shop, not so much <grin>)Lloyd I'm not much experienced with titrating. I'm somewhat familiar with the concept, but not the details of titration for highly accurate pH measurement. Could you explain it in enough detail that I could do it on my own? I need to know the setup, equipment (some of which I probably already have), reagents (their quantity and concentrations) and procedures. I know I'm asking a lot, but I want to do it accurately and properly. You can PM me if you prefer. Thanks. WSM
lloyd Posted December 2, 2016 Posted December 2, 2016 "Could you explain it in enough detail that I could do it on my own?"--------------I can only describe it generally, because I haven't had the need to do it in about 45 years! An indicator is added to the sample. Titration involves using 'calibrated' (known Normal-concentrations) of acid and/or base solutions to neutralize the sample. The titration rig allows mere droplets of the solutions to be added the sample, such that the neutralization point is arrived-at accurately. Calibration marks on the titration columns allow you to accurately determine exactly how much of one or both solutions were used to do that. Calculations based upon the concentration of the solutions then allow you to determine the pH of the sample. It's been a while for me! I actually HAVE one in my glassware storage, but haven't had the need to use it since I've been in the professional pyro business. Lloyd
OldMarine Posted December 3, 2016 Posted December 3, 2016 I'm pretty sure I have some self zeroing burettes here somewhere. They were originally purchased for bio-diesel testing so would probably be of convenient size for pyro uses. I'm no scientist but I have an in on glassware and other lab equipment who hooks me up occasionally at the end of a project. If ya'll figure out what would be needed to build a titration setup, holler at me before you buy anything.I think I posted a pic of some of my acquisitions here or on FW.
WSM Posted December 3, 2016 Posted December 3, 2016 "Could you explain it in enough detail that I could do it on my own?"--------------I can only describe it generally, because I haven't had the need to do it in about 45 years!An indicator is added to the sample.Titration involves using 'calibrated' (known Normal-concentrations) of acid and/or base solutions to neutralize the sample. The titration rig allows mere droplets of the solutions to be added the sample, such that the neutralization point is arrived-at accurately.Calibration marks on the titration columns allow you to accurately determine exactly how much of one or both solutions were used to do that. Calculations based upon the concentration of the solutions then allow you to determine the pH of the sample.It's been a while for me! I actually HAVE one in my glassware storage, but haven't had the need to use it since I've been in the professional pyro business.Lloyd Thanks, Lloyd. Your description isn't super detailed, but I get it. I think I can use it as a guide to develop a system to determine the exact pH of the electrolyte, depending on which indicator is required and it's availability. WSM
WSM Posted December 3, 2016 Posted December 3, 2016 I'm pretty sure I have some self zeroing burettes here somewhere. They were originally purchased for bio-diesel testing so would probably be of convenient size for pyro uses. I'm no scientist but I have an in on glassware and other lab equipment who hooks me up occasionally at the end of a project. If ya'll figure out what would be needed to build a titration setup, holler at me before you buy anything.I think I posted a pic of some of my acquisitions here or on FW. That's awesome, OldMarine. I'll take you up on that offer, when I need some special glassware. Thanks. WSM
WSM Posted December 4, 2016 Posted December 4, 2016 (edited) My thought is to build an external framework to hold a compatible top and bottom plate to the ends of the pipe, to form a tank. The pipe section will be standing vertically on one end, and have piping running mainly through the flat plates rather than negotiating the curved sides of the pipe tank wall. A stand of some sort will add stability to the structure and rise it high enough to allow plumbing, electrode and sensor fittings to enter and leave the bottom of the tank as well as the top. The concept cell development is shaping up to resemble a vertical tie rod cylinder. My thinking is to clamp compatible, flat plates to the top and bottom flat ends of the PVDF tank, using stainless steel threaded rods running the length of the tank and held securely with stainless steel nuts and flat washers. I'm thinking of covering the threaded rods with PVC pipe to prevent cuts from incidental contact with them. If I run the tie rods longer on the bottom of the tank to a wide base plate, they'll make a stable foundation for the cell and allow for plumbing the bottom as well as the top of the cell. I'm still debating whether to circulate the electrolyte from a compatible tank, positioned at a lower level, using a chemical handling pump. The attraction of the notion is, if a power outage occurs, the reaction chamber will drain back down to the holding tank, leaving the electrodes unexposed to the damaging effects of the electrolyte while the power is off. The main problem is, if that happens, sodium chlorate crystals will drop out of solution, requiring a cleanout of the holding tank and a fresh startup of the cell when the power resumes. I think I can design something to handle that. Power outages here are rare, but do occur. Another option may be to arrange a UPS to keep things running in the event of a power outage. Fortunately, the majority of power service interruptions here tend to be of a short duration. Realistically, you can't plan for everything; but the majority of the time our electricity here runs reliably. WSM Edited December 5, 2016 by WSM
WSM Posted December 7, 2016 Posted December 7, 2016 Does anyone know where I can get two pieces of PTFE (Teflon) plate, 8" x 8" x 1/2" thick (200 mm x 200 mm x 12.7 mm), for a reasonable cost? With those I can make progress with my high temperature NaClO3 cell, otherwise I'm stuck. PVDF would work also, but may be harder to get than Teflon. Any leads would be greatly appreciated. Thanks. WSM
lloyd Posted December 7, 2016 Posted December 7, 2016 "reasonable cost" and "1/2-inch thick PTFE" aren't compatible characteristics. The going rate for 1/2" 6x6 sheets is around $80 USD. The only place you'll find it cheaper will be in a salvage operation. Lloyd
WSM Posted December 7, 2016 Posted December 7, 2016 (edited) "reasonable cost" and "1/2-inch thick PTFE" aren't compatible characteristics. The going rate for 1/2" 6x6 sheets is around $80 USD. The only place you'll find it cheaper will be in a salvage operation.LloydSalvage is okay, as long as the material is sound and uncompromised. Thanks for the response. WSM Anyone know of anything compatible out there? Edited December 8, 2016 by WSM
WSM Posted December 8, 2016 Posted December 8, 2016 (edited) If there's no PVDF or PTFE plate available at an affordable cost, I may try some 1/2" (12.7 mm) thick CPVC plate (rated to 93oC) instead. Though the goal is to run it up to 20oC higher than that, it may well tolerate it for the duration of my test (maybe). To be determined... WSM Edited December 9, 2016 by WSM
WSM Posted December 9, 2016 Posted December 9, 2016 (edited) If there's no PVDF or PTFE plate available at an affordable cost, I may try some 1/2" (12.7 mm) thick CPVC plate (rated to 93oC) instead. Though the goal is to run it up to 20oC higher than that, it may well tolerate it for the duration of my test (maybe). To be determined...WSM I found amongst some of my early acquisitions of PVDF materials, some flat plate remnants, just large enough to fit the 6" schedule 80 PVDF pipe and seal the ends to make the reaction vessel I need for the next part of my sodium chlorate experiments. Next, I need to get the stainless steel threaded rod, nuts and fender washers to assemble the high temperature cell. I'm looking forward to seeing this part of my research get built and operate. WSM Edited December 10, 2016 by WSM
pyrojig Posted December 10, 2016 Posted December 10, 2016 Ah the thread gets juicy again. . This sounds like a well thought out setup , one im wanting to see.
WSM Posted December 10, 2016 Posted December 10, 2016 Ah the thread gets juicy again. . This sounds like a well thought out setup , one im wanting to see. Hey, come on out and see it. No one here "gets it"; they think it's just a collection of "more of my junk" . They don't understand that creativity has a beauty of it's own ! WSM
PTFE Posted December 11, 2016 Posted December 11, 2016 (edited) Hey guys After some time i can give you some explenation about my cell.Unfortunately i have deleted all pictures of my previous cells.My first cell was a bottling jar with a pvc plate on top, pressed down with a screw clamp.The cell was only to prove if the MMO i found at work could be used.It exploded because i didnt ensure, that the electrodes wont touch each other. But after all the MMO seems usable andi started to built proper cells. On ebay i got this nice piece of ptfe (it endet up with 50$ or so)and for another 30$ i got a round d=155mm*50mm pice to seal it up.after working on the lathe, purchasing some V4A screws and some 1mm ptfe sheet for the insulation rings, i finally got my cellbody done. For my mesh type electrodes i choose spot welding to connect them to the titanium stripes. But at first i had to built a spot welder.An old MOT(microwaveoventransformer) was dismantled and a new secondary was built out of flat copper.(thick wire will also do the job)with some sharpened copper rods i welded the electrodes and the cell was ready for the first run after the run i had to admit that the 5mm boro.tube isnt enough to take the gases from 100A and also the filling level indication doesnt work really well. so i added a ptfe venting tube with 15mm inner diameter, which also gives more stability.The tube for level indication was replaced with a thicker one and the top was connected to the cell to provide a closed loop but it did not help that much.Filling level indication will work when i use only salt in solution.. but in my case i got some unsolved salt and later crystalised naclo3 which blocks the entry of the indication tube...but i dont really care about because i fill my cell that high, that some of the electrolyte is pumped up the venting hose.This provides also a cooling effect and a better mixing of the gases with the electrolyte. It also brings the advantage that you have a reservoir of electrolyte which slowly decreases. after this run i had some problems to get out the electrodes.but finaly i was stronger.now i have to rebuilt the coolingtube Finally it was a good run..with total 1000g of nacl, 90kWhrs and 0,5l 30%Hcl in 3 days i endet up with thisYou also see a new electrode array here.. The array is for another little cell. I hope you can get some inspiration. I found amongst some of my early acquisitions of PVDF materials, some flat plate remnants, just large enough to fit the 6" schedule 80 PVDF pipe and seal the ends to make the reaction vessel I need for the next part of my sodium chlorate experiments. Next, I need to get the stainless steel threaded rod, nuts and fender washers to assemble the high temperature cell. I'm looking forward to seeing this part of my research get built and operate. WSM It looks like our sells will get quite similar greetings,PTFE Edited December 11, 2016 by PTFE
WSM Posted December 11, 2016 Posted December 11, 2016 (edited) Hey guys After some time i can give you some explenation about my cell.Unfortunately i have deleted all pictures of my previous cells.My first cell was a bottling jar with a pvc plate on top, pressed down with a screw clamp.The cell was only to prove if the MMO i found at work could be used.It exploded because i didnt ensure, that the electrodes wont touch each other. But after all the MMO seems usable andi started to built proper cells.IMG-20160317-WA00011.jpgOn ebay i got this nice piece of ptfe (it endet up with 50$ or so)and for another 30$ i got a round d=155mm*50mm pice to seal it up.IMG-20160317-WA0005.jpgafter working on the lathe, purchasing some V4A screws and some 1mm ptfe sheet for the insulation rings, i finally got my cellbody done.IMG-20160419-WA0000.jpgFor my mesh type electrodes i choose spot welding to connect them to the titanium stripes. But at first i had to built a spot welder.An old MOT(microwaveoventransformer) was dismantled and a new secondary was built out of flat copper.(thick wire will also do the job)IMG-20160227-WA0001.jpgwith some sharpened copper rods i welded the electrodesIMG-20160228-WA0008.jpgIMG-20160228-WA0006.jpgand the cell was ready for the first run IMG-20160424-WA0001.jpgafter the run i had to admit that the 5mm boro.tube isnt enough to take the gases from 100A and also the filling level indication doesnt work really well.so i added a ptfe venting tube with 15mm inner diameter, which also gives more stability.The tube for level indication was replaced with a thicker one and the top was connected to the cell to provide a closed loop but it did not help that much.DSC_0314.JPGFilling level indication will work when i use only salt in solution.. but in my case i got some unsolved salt and later crystalised naclo3 which blocks the entry of the indication tube...but i dont really care about because i fill my cell that high, that some of the electrolyte is pumped up the venting hose.This provides also a cooling effect and a better mixing of the gases with the electrolyte. It also brings the advantage that you have a reservoir of electrolyte which slowly decreases.IMG-20160905-WA0024.jpgDSC_0316.JPGafter this run i had some problems to get out the electrodes.but finaly i was stronger.DSC_1141.JPGDSC_1143.JPGnow i have to rebuilt the coolingtube DSC_1142.JPGFinally it was a good run..with total 1000g of nacl, 90kWhrs and 0,5l 30%Hcl in 3 days i endet up with thisDSC_1146.JPGYou also see a new electrode array here..DSC_1147.JPGThe array is for another little cell.DSC_1176.JPGDSC_1175.JPGI hope you can get some inspiration.It looks like our sells will get quite similar greetings,PTFE Nice job, PTFE. Other than us using different fluoropolymers, I see many similarities also. I do prefer the round leads to the flat straps so many amateurs use, so that I can seal the leads in compatible compression fittings (preventing salt creep, amongst other problems). If I had access to the materials you've found, I'd probably have done the same as you did with your cell (I like it). Your yield looks good. Nice white crystals of chlorate. Did you purify the salt before running the cell? Keep us informed of your progress. It's exciting to see someone else doing similar work. WSM Edited December 11, 2016 by WSM
eb666 Posted December 12, 2016 Posted December 12, 2016 Hey guys, after all of my electrolysis is done, I am now at the step in cleaning out my perc solution and get rid of the remaining chlorate. Adding slowly the solution of metabisulfite created a heavy reaction. As I am calculating with a theoretical maximum of 1400g perchlorate in my liquor, I dissolved 150g of sodium metabisulfite to in about 600ml of destilled water, made my liquor to pH 3 and then added slowly the metabisulfite and checked for chlorate in several steps. The indigo carmine test still reacts with clear spots which always indicate chlorate present - and that regardless of the fact, that I added the whole solution of 150g metabisulfite. It seems, that I get a false positive test. How do you guys indicate chlorate with the indigo carmine spot test? What if I add "too much" metabisulfite? Can it also destroy my perchlorate? I have no possibilty to get NPAA. What should I do now? Thank you and kind regards Theo Destroying chlorate in perchlorate solutions only makes sense if the amounts of chlorate are reasonaly small. You may have 10% ? 15% ? chlorate. This is far too much. Get an idea of how much chlorate you have. Take a small amount of the solution and evaporate to dryness and test the chlorate/perchlorate mixture by dropping some concentrated sulphuric acid on it. If you get ignition or alot of crackling you have TOO MUCH chlorate still present. Either run and run the cell (not advisable with platinum anode) using lead dioxide (if you have lead dioxide) or recrystallize. A great way to get an idea of how much chlorate you have is to use Hydrochloric acid as a test on some of the diluted solution. See here for details (3 test tubes, down the page somewhat, with yellow colours showing) http://oxidizing.typhoonguitars.com/chlorate/tests.html Indigo carmine test here.http://oxidizing.typhoonguitars.com/chlorate/so2pat.html More detail on indigo carmine test herehttp://oxidizing.typhoonguitars.com/chlorate/indigo.gif There is no need to titrate chlortte solutions to get exact pH. No need for a pH meter either. The pH efficiency curve is quite blunt (as opposed to a spike) and the adding-acid/chlorine-escapeing thing is self regulating. Just add acid at the recommended rate.
Arthur Posted December 12, 2016 Posted December 12, 2016 One patent said that a chlorate/perchlorate mix (sodium salts) was mixed with KCl and the K perc precipitated first, when all the KPerc was ppt out, THEN the K Chlorate would PPT out. The different crystal shapes made it obvious where to stop!
WSM Posted December 13, 2016 Posted December 13, 2016 (edited) One patent said that a chlorate/perchlorate mix (sodium salts) was mixed with KCl and the K perc precipitated first, when all the KPerc was ppt out, THEN the K Chlorate would PPT out. The different crystal shapes made it obvious where to stop!Now that's an interesting concept. That would also be a good skill to have (knowing when to stop adding the potassium chloride solution). WSM Edited December 13, 2016 by WSM
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