oldmanbeefjerky Posted June 16, 2011 Share Posted June 16, 2011 (edited) progress with the lead is slow, what i though initially, was the lead acitate being formed, was actually the lead catalytically decomposing the hydrogen peroxide. ill post some pics right now.the copper acetate on the other hand is doing well, it has already picked up a full blue (not light not dark), tinge . once im done ill post a flash slideshow of the whole proccess. -edit- the reaction with lead is unfortunately very slow even with hydrogen peroxide, as it doesnt work for very long. though all the dispersed lead (floating in water giving that grey tinge)does convert into yellow lead oxide as soon as any peroxide is added,but unfortunately not on the actual lead lumps though, i just came to realise that when making lead dioxide electrodes by sulfuric acid oxidization, the acid is just a catalyst , and short of contaminants neutralising the acid, and bubbles spattering out the acid solution, no acid is lost during the electrolysis. all thats needed is two peices of lead and sulfuric acid, how pure doesnt matter, but its super easy to make for that purpose, just electrolyse copper sulfate 50g in 100ml of water, then filter, then electrolyse with two lead electrodes, and done. one becomes lead dioxide, the other doesnt change at all. Edited June 16, 2011 by oldmanbeefjerky Link to comment Share on other sites More sharing options...
oldmanbeefjerky Posted June 23, 2011 Share Posted June 23, 2011 (edited) i now have several lead electrodes i smelted.i am going to find out, if using lead electrodes to electrolysis copper sulfate will work to make sulfuric acid and lead dioxide.wish me luck XD also, i was temporarily successful in creating a lead dioxide electrode by electrolyzing sulfuric acid i made form 30g of copper sulfate, but it was clean sulfuric acid, with no contaminants .before i blew up the cheap battery charging 12v 500ma power supply, i plated a lead cathode with lead dioxide, and it appeared to have a rather sturdy layer of lead dioxide coating it, half could be rubbed off, the other was attached as strongly as rust on an iron bar. ill need to borrow my friends ATX power supply to continue the electrolysis (this is the same friend who trolled here under my preferred username jpoopdog, a few months back). hopefully though i will be able to make the lead dioxide layer thicker with a lower voltage making less bubbles and this time for more than 4 hours! the lead acetate is still not going that fast. a white crust appeared but i was too afraid to taste test it to confirm whether or not is was lead acetate or not. though considering that there is nothing else that could make the crust, i think it is lead acetate. ill give it a few more days before i filter it all out and boil down the solution, to find out just how much i got. all the acid however has been used up, and the solution is now soapy, which seems rather good considering acids wont allow water to become soapy unless neutralized, if im lucky, it wont be destroyed vinagar, but infact the lead acetate! Edited June 23, 2011 by oldmanbeefjerky Link to comment Share on other sites More sharing options...
Mumbles Posted June 23, 2011 Share Posted June 23, 2011 The easiest way to test for lead acetate is to taste it. It's apparently incredibly sweet. Or I suppose you could take the easy way out and mix it with table salt. Link to comment Share on other sites More sharing options...
superstring Posted June 23, 2011 Share Posted June 23, 2011 I cannot imagine why anyone who is trying to create KClO4 for pyro uses would attemp this. At today's prices this just seems like a total waste of time. I'm sure you can still buy it in Florida! Link to comment Share on other sites More sharing options...
Mumbles Posted June 23, 2011 Share Posted June 23, 2011 Most people who take this seriously either are science nerds, or live outside of the US (often both). It's not nearly as available outside of the US. Link to comment Share on other sites More sharing options...
oldmanbeefjerky Posted June 24, 2011 Share Posted June 24, 2011 (edited) I am more of the latter. And i think since its safe enough to consider using a taste test, i think on its next formed crust, if there is one at all, ill do a taste test. By the way, does anyone know what formaldehyde tastes like, my friend told me last night that there is a possibility that it would have formed when i added the peroxide to the vinegar lead solution. also, since i plan to sell my lead acetate along with copper acetate for the lowest possible price, and considering i can get free lead and super cheap acetic acid, i would rather make my own than buy some. -edit- i just tasted the lead acetate and it was very very sweet, but also very dry. i just realised that if a crystal crust is forming, i must have a saturated solution of lead acetate, and since i have 150ml, there must be 66g of lead acetate there( 44g / 100ml), which i aquired faster than if i had bought it online, and cheaper, as the total vinegar costs are under a dollar!still, i will try to get more to form to be sure its saturated Edited June 24, 2011 by oldmanbeefjerky Link to comment Share on other sites More sharing options...
Mumbles Posted June 24, 2011 Share Posted June 24, 2011 I have my doubts if it's forming paraformaldehyde. Firstly, aldehydes are a reduced form of acids, and you're adding an oxidizer. Secondly, formaldehyde is 1 carbon shorter than acetic acid. Forming Peracetic acid however is very reasonable and likely, but that decomposes before too long. You can stabilize it (it's the basis for some color safe bleach), but normally in a lab it's made in situ as needed from acetic acid and peroxide. Link to comment Share on other sites More sharing options...
WSM Posted June 24, 2011 Share Posted June 24, 2011 I am more of the latter. And i think since its safe enough to consider using a taste test, i think on its next formed crust, if there is one at all, ill do a taste test. By the way, does anyone know what formaldehyde tastes like, my friend told me last night that there is a possibility that it would have formed when i added the peroxide to the vinegar lead solution. also, since i plan to sell my lead acetate along with copper acetate for the lowest possible price, and considering i can get free lead and super cheap acetic acid, i would rather make my own than buy some. -edit- i just tasted the lead acetate and it was very very sweet, but also very dry. i just realised that if a crystal crust is forming, i must have a saturated solution of lead acetate, and since i have 150ml, there must be 66g of lead acetate there( 44g / 100ml), which i aquired faster than if i had bought it online, and cheaper, as the total vinegar costs are under a dollar!still, i will try to get more to form to be sure its saturated Excellent work OMBJ! I hope you spit it out after tasting . They don't call it "sugar of lead" for nothing. The ancient Romans used to add a little to their wine to sweeten it (which might answer the question about the fall of their empire ). It would be nice to see those photos, though (hint, hint!). Thanks for sharing your experiences and thoughts. WSM Link to comment Share on other sites More sharing options...
WSM Posted June 24, 2011 Share Posted June 24, 2011 Most people who take this seriously either are science nerds, or live outside of the US (often both). It's not nearly as available outside of the US. ...and for all we know, not for much longer in the USofA :blink:! Better to develop the electrochemical skills before you need them ! (not totally tongue-in-cheek) WSM Link to comment Share on other sites More sharing options...
WSM Posted June 24, 2011 Share Posted June 24, 2011 I cannot imagine why anyone who is trying to create KClO4 for pyro uses would attemp this. At today's prices this just seems like a total waste of time. I'm sure you can still buy it in Florida! ...But everyone doesn't live in Florida (and some of our number don't live in the US). WSM Link to comment Share on other sites More sharing options...
oldmanbeefjerky Posted June 24, 2011 Share Posted June 24, 2011 including ME! also mumbles i think your right as initially a giant conglomerate blob of jelly formed in my copper acetate solution when i attempted to electrolyse copper in a vinagar peroxide solution. though i havent had the problem with the lead acetate thank god! also, the photos i have now dont really differ enough from the ones posted before. ill turn down the resolution of my camera and take some more pics of my various copper acetate solutions and my lead acetate crust as soon as it forms again. wordof warning to anyone trying this. always set at least 500ml of volume aside in your container when making lead acetate by lead vinagar and peroxide method, or else your mix will overflow with foam from the formed formaldehyde and other gelatinous gels, as well as the actual lead acetate.later too i will add more peroxide to the solution to show you exactly why.(photo) Link to comment Share on other sites More sharing options...
Bonny Posted June 28, 2011 Share Posted June 28, 2011 WSM, did you ever try the LD anode from Patsroom? I'm just getting mine set up. I haven't decided on which of my power supplies to use. I can use the PC unit which will deliver about 25A @ 5V, or I can use the battery charger, getting about 10A and ~6V. I'll hopefully get it running this weekend. I've got quite a lot of KClO3 feedstock ready. Mounting the LD anode has been a bit of a PITA, as the strap is so narrow, I love the nice 1" straps on my electrodes from Swede... Link to comment Share on other sites More sharing options...
WSM Posted June 29, 2011 Share Posted June 29, 2011 WSM, did you ever try the LD anode from Patsroom? I'm just getting mine set up. I haven't decided on which of my power supplies to use. I can use the PC unit which will deliver about 25A @ 5V, or I can use the battery charger, getting about 10A and ~6V. I'll hopefully get it running this weekend. I've got quite a lot of KClO3 feedstock ready. Mounting the LD anode has been a bit of a PITA, as the strap is so narrow, I love the nice 1" straps on my electrodes from Swede... Hi Bonny, Sadly, no. Mine came with the LD on the top cross strap chipped off. It's not the end of the world since I plan to spot weld a tubular lead (and fill it with lead-free solder) to the top strap to take the place of the whimpy lead it came with. The second one I bought has a wider and thicker strap with a ~1/4" hole in it for connecting to power. Unfortunately, it has worse chipping in bad spots. I hope I can seal the chips with something that will prevent moisture getting in and delaminating the LD from the Ti substrate. I was considering using a paste made from Viton and dehydrated acetone to seal the chips. I'm thinking the best way to go is converting sodium chlorate to sodium perchlorate, then double decomposition with potassium chloride to potassium perchlorate and sodium chloride. I was concerned about sodium contamination, but dissolving and recrystallizing the created KClO4 should do an excellent job of purifying the end product. Crystallization is nature's way of purifying salts, and it works very well. For potassium chlorate, it's simple enough to convert KCl to KClO3 without much fuss. The perchlorate works better with sodium because of the solubilities involved. Where potassium perchlorate will want to drop out of solution almost as soon as it's formed, sodium perchlorate is more soluble than sodium chlorate and sodium chlorate is more soluble than sodium chloride. When I get the experimental system running and prove the ideas I'm researching, I plan to get back to The Monster and think I'll convert the experimental system to a continuous sodium system (to create stock for an experimental perchlorate system using the LD anodes I've bought). So many ideas to prove (or disprove) and so little time... WSM Link to comment Share on other sites More sharing options...
ZenBlaster Posted June 29, 2011 Share Posted June 29, 2011 from what i understand, if you add hydrogen peroxide to potassium chlorate, it would add another oxygen molecule, forming potassium perchlorate, now, you would want to boil as much water out of the hydrogen peroxide as you can to get a finished product that contains less contaminants, but there still is going to be some, so if you really want high grade perchlorate, i would just buy it online. Link to comment Share on other sites More sharing options...
Bonny Posted June 29, 2011 Share Posted June 29, 2011 Hi Bonny, Sadly, no. Mine came with the LD on the top cross strap chipped off. It's not the end of the world since I plan to spot weld a tubular lead (and fill it with lead-free solder) to the top strap to take the place of the whimpy lead it came with. The second one I bought has a wider and thicker strap with a ~1/4" hole in it for connecting to power. Unfortunately, it has worse chipping in bad spots. I hope I can seal the chips with something that will prevent moisture getting in and delaminating the LD from the Ti substrate. I was considering using a paste made from Viton and dehydrated acetone to seal the chips. I'm thinking the best way to go is converting sodium chlorate to sodium perchlorate, then double decomposition with potassium chloride to potassium perchlorate and sodium chloride. I was concerned about sodium contamination, but dissolving and recrystallizing the created KClO4 should do an excellent job of purifying the end product. Crystallization is nature's way of purifying salts, and it works very well. For potassium chlorate, it's simple enough to convert KCl to KClO3 without much fuss. The perchlorate works better with sodium because of the solubilities involved. Where potassium perchlorate will want to drop out of solution almost as soon as it's formed, sodium perchlorate is more soluble than sodium chlorate and sodium chlorate is more soluble than sodium chloride. When I get the experimental system running and prove the ideas I'm researching, I plan to get back to The Monster and think I'll convert the experimental system to a continuous sodium system (to create stock for an experimental perchlorate system using the LD anodes I've bought). So many ideas to prove (or disprove) and so little time... WSM My LD anode looks pretty good, no visible damage. You are right about the wimpy strap...maybe 3/8" wide. I have it mounted, just waiting on my silicone seal to cure. I will be using KClO3 though, as that's what I have. The KClO4 does drop out as it is formed, I made a few lbs last year using Pt anodes (fried 2 of them running the cell too long I think) I lmow you can't get nearly as much in a cell as when using sodium, but I have soo much KClO3 that I'll never use otherwise. What do you think I should use as the power supply? The PC unit or the charger? from what i understand, if you add hydrogen peroxide to potassium chlorate, it would add another oxygen molecule, forming potassium perchlorate, now, you would want to boil as much water out of the hydrogen peroxide as you can to get a finished product that contains less contaminants, but there still is going to be some, so if you really want high grade perchlorate, i would just buy it online. I've never heard anyone using peroxide to convert chlorate to perc. I think if it was feasable, someone would be doing it. Anyway, IMO "high grade" and better than a lot of commercial product can be easily produced. Check out Swede's blogs for some good info that works...and read this entire thread. Link to comment Share on other sites More sharing options...
Mumbles Posted June 29, 2011 Share Posted June 29, 2011 In theory hydrogen peroxide (potential of around 1.8V) can oxidize chlorate to perchlorate (potential around 1.22V). However, there is this pesky thing called the real world where it doesn't work. I haven't seen any reasoning for why it doesn't work, but I've seen several people confirm that it does not. It may require a higher over potential than peroxide can supply. After all, you need several volts to do it electrolytically. That however has other factors, such as oxidizing chlorate instead of producing oxygen. I've seen references to certain oxidants being able to do it, such as persulfates and presumably peroxysulfates. However, this is far from a clean or complete conversion. As a small correction, it'd be adding an atom of oxygen, not a molecule. ClO5- (despite what oldmanbeefjerky may say) does not exist under real world conditions. Link to comment Share on other sites More sharing options...
WSM Posted June 29, 2011 Share Posted June 29, 2011 I have soo much KClO3 that I'll never use otherwise. What do you think I should use as the power supply? The PC unit or the charger? Hi Bonny, But KClO3 is so useful. It comes in handy for color smokes, H-3 and E-match pyrogen (oxidizer). Oh well, you should go with your feelings and tolerance for risk. Which supply? That's a tough question. The ideal would be between 6-7 Vdc and variable current (0-100 amps, for example). I suppose the best answer is to experiment with what you have or have access to. On the other hand, If you have two LD anodes, wire them in series and use the PC power supply on the 12 Vdc output . Let us know what you decide and the results. Good luck . WSM Link to comment Share on other sites More sharing options...
ZenBlaster Posted June 29, 2011 Share Posted June 29, 2011 In theory hydrogen peroxide (potential of around 1.8V) can oxidize chlorate to perchlorate (potential around 1.22V). However, there is this pesky thing called the real world where it doesn't work. I haven't seen any reasoning for why it doesn't work, but I've seen several people confirm that it does not. It may require a higher over potential than peroxide can supply. After all, you need several volts to do it electrolytically. That however has other factors, such as oxidizing chlorate instead of producing oxygen. I've seen references to certain oxidants being able to do it, such as persulfates and presumably peroxysulfates. However, this is far from a clean or complete conversion. As a small correction, it'd be adding an atom of oxygen, not a molecule. ClO5- (despite what oldmanbeefjerky may say) does not exist under real world conditions. well, in that case, i think i'll buy it, i have neither the patience nor the desire to build expensive electronics myself, possibly when i have my own place and a better source of income, but for now, i think i'll leave the chemistry to the chemists. Link to comment Share on other sites More sharing options...
Mumbles Posted June 29, 2011 Share Posted June 29, 2011 Trust me, I wish it wasn't so. Perhaps they were not trying a concentrated enough peroxide to do the trick. It could just be a pH thing as well. For the persulfate oxidation I know they make the solution quite basic first. Link to comment Share on other sites More sharing options...
ZenBlaster Posted June 29, 2011 Share Posted June 29, 2011 Trust me, I wish it wasn't so. Perhaps they were not trying a concentrated enough peroxide to do the trick. It could just be a pH thing as well. For the persulfate oxidation I know they make the solution quite basic first. well, i based this idea off of a video i saw, basically, if you took powdered potassium chlorate, boiled the water out of some hydrogen peroxide, added it to the powder, added rubbing alcohol until the solution was a liquid, then let it evaporate out, you would end up with potassium perchlorate crystals. Link to comment Share on other sites More sharing options...
WSM Posted June 29, 2011 Share Posted June 29, 2011 My LD anode looks pretty good, no visible damage. You are right about the wimpy strap...maybe 3/8" wide. I have it mounted, just waiting on my silicone seal to cure. I will be using KClO3 though, as that's what I have. The KClO4 does drop out as it is formed, I made a few lbs last year using Pt anodes (fried 2 of them running the cell too long I think) I lmow you can't get nearly as much in a cell as when using sodium, but I have soo much KClO3 that I'll never use otherwise. Hi Bonny, Congratulations on getting an undamaged electrode, I wasn't near so lucky (twice!). My main concern about using KClO3 for feed stock, especially with a mesh type anode, is the electrode getting fouled with the perchlorate crystals formed. I could see this condition in the photos Swede posted and have thought about it ever since. Now if our LD anodes were solid maybe this concern would vanish? I don't know. If we start with NaCl and make NaClO3 (which is more soluble than the NaCl) and then make NaClO4 (which is more soluble than NaClO3) we have the happiest condition, except for sodium contamination; but again, the crystalization process combined with proper rinsing can eliminate sodium from the final product (KClO4) after double decomposition with KCl. I'll have to try it and see. WSM Link to comment Share on other sites More sharing options...
Bonny Posted June 29, 2011 Share Posted June 29, 2011 Hi Bonny, Congratulations on getting an undamaged electrode, I wasn't near so lucky (twice!). My main concern about using KClO3 for feed stock, especially with a mesh type anode, is the electrode getting fouled with the perchlorate crystals formed. I could see this condition in the photos Swede posted and have thought about it ever since. Now if our LD anodes were solid maybe this concern would vanish? I don't know. If we start with NaCl and make NaClO3 (which is more soluble than the NaCl) and then make NaClO4 (which is more soluble than NaClO3) we have the happiest condition, except for sodium contamination; but again, the crystalization process combined with proper rinsing can eliminate sodium from the final product (KClO4) after double decomposition with KCl. I'll have to try it and see. WSM I never had any fouling with my mesh Pt anode making KClO4 from KClO3, but the holes were much larger than this LD anode. I'll see hoe it works. I use a bubbler in the cell and maybe having the bubbles running up the anode might keep it cleaner... hopefully will have the cell up this weekend. Link to comment Share on other sites More sharing options...
WSM Posted June 30, 2011 Share Posted June 30, 2011 I never had any fouling with my mesh Pt anode making KClO4 from KClO3, but the holes were much larger than this LD anode. I'll see hoe it works. I use a bubbler in the cell and maybe having the bubbles running up the anode might keep it cleaner... hopefully will have the cell up this weekend. Awesome! Keep us up to date with your progress (and take photos, too, if you can). Thanks. WSM Link to comment Share on other sites More sharing options...
pdfbq Posted June 30, 2011 Share Posted June 30, 2011 (edited) @Bonny I would stick to your computer power supply, gut feeling. A lower and 'smoother' voltage keeps your anodes in better shape I guess. I have experience with making perc with 5.2V and it runs perfectly. I did about (forgot exactly numbers) 1 kilo NaClO3 to perc in 5 days or so on 5.2 V (I have now about 10 kilos, so I have enough for a while ) Edited June 30, 2011 by pdfbq Link to comment Share on other sites More sharing options...
Bonny Posted June 30, 2011 Share Posted June 30, 2011 @Bonny I would stick to your computer power supply, gut feeling. A lower and 'smoother' voltage keeps your anodes in better shape I guess. I have experience with making perc with 5.2V and it runs perfectly. I did about (forgot exactly numbers) 1 kilo NaClO3 to perc in 5 days or so on 5.2 V (I have now about 10 kilos, so I have enough for a while ) I'll do that then. I can't remember the voltage I was getting (chlorate cell),but IIRC correctly is was ~4.8-4.9V. I'm trying to find my notes... Link to comment Share on other sites More sharing options...
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